March 18th (Sat), 2017
Hiyoshi Campus, Keio University, Yokohama, Kanagawa, JapanThe Chemical Society of Japan & The Chinese Chemical SocietyWelcoome to Japan!
J!
Dear Coolleagues
Globalizzation is thet
proce
ess of inte
ernational
integ
gration arrising fromm the inte
erchange of world
view
ws, products, ideas, an
nd other asspects of culture.
Particulaarly, collab
borations betweenbchhemists ofvario
ous countries often transcend bordersbannd cultural
diffe
erences. The
T
fundamental nature of chemical
scien
nce allow
ws chemissts to coommunicate usingknow
wledge of their field
d. Its foccus is on chemistry
students and chemists interested
d in deve
eloping a
glob
bal approacch to open
n new scien
nce and technology,
by participatinpg in an intternational symposium. Overa
all, multidissciplinary isi thepasssword for the successsful globaliization of chemistry.
c
The Cheemical Sociiety of Japan (CSJ) is delighted to be co-oorganizing with
the ChineseCCh
hemical So
ociety (CCSS) at the occasionooff 97th Ann
nual Meetin
ng of
Chem
mical Socieety of Japa
an at Yoko
ohama. I am confident that mmultidiscipllinary
resea
arch can be develope
ed throughh this interrnational jooint forum..
I would like to tha
ank Prof. Biao Yu, rep
presenting CCS as Ch
hairs, as we
ell asProf Koichi Fukase and Prof.
P
Takayyuki Doi, reepresentin
ng CSJ as C
Chairs, for theirgrea
at effort to make CCS
S-CSJ young chemistss’ forum po
ossible.
Mutual exchangee and colllaborationn among chemists between two
coun
ntries havee continued
d ever afte
er, even wh
hen the flo
ow of know
wledge beccame
no longerlone
e-sided, as it was ini early daays, and haveh
led tto tremendous
conttributions tot the deve
elopment ofo new cheemistry.
It is ourr great ple
easure andd honor too add neww pages too the history ofmutu
ual exchan
nge betweeen global countries.
cProfesso
or Hisashi YamamotoYoPresidennt;
The Cheemical Sociiety of JapaanThe 7th CCS‐CSJ Young Chemists Forum 2017
―Frontier in Organic Synthesis toward Middle Molecular Strategy
The Chemical Society of Japan The 97th Annual Meeting■Date■VenueMarch 18th (Saturday), 2017 9:00‐17:40
S2; Room J24, House B, Bldg. 4,
Hiyoshi Campus, Keio University, Yokohama, Kanagawa, Japan■Hosted by The Chemical Society of Japan & The Chinese Chemical Society

09:00

Opening Remarks

Representative from CSJ
Hisashi Yamamoto
President of the CSJ

09:05

Introductory Talk

Koichi Fukase,
Osaka University

…2

09:10

Aromatic Molecules: Decarbonylative Coupling andMultiple Arylation

Junichiro Yamaguchi,
Waseda University

…3

09:40

C‐H Functionalization Strategy for Chemical Synthesisof α‐Amino Acids and Complex Peptides

Gong Chen,
Nankai University

…5

10:10

Coffee break

10:20

Synthesis and Biological Evaluation of Antibiotic
Polyketides

Yoko Saikawa,
Keio University

…7

10:50

Natural Product Synthesis Facilitated by Ligand Design

Wenjun Tang,
Shanghai Institute ofOrganic Chemistry

…9

11:20

Synthesis of Monomers for Spectomycin B1,
A Middle Size SUMOylation Inhibitor Molecule

Go Hirai,
Kyushu University

…11

11:50

Lunch

13:10

Remote Activation of O/S‐Benzyl Glycosides in
Latent‐Active Glycosylation

Qian Wan,
Huazhong Univ. of
Science and Technology

…13

13:40

Development of the Novel Cancer Immunotherapy
Utilizing α‐Gal

Yoshiyuki Manabe, et al.
Osaka University

…15

14:10

Type II Intramolecular [5+2] Cycloaddition

Chuang‐Chuang Li,
South Univ. of Science &Technology of China…17

Ken Ohmori,Tokyo Institute ofTechnology…19

Products: Shuanhu Gao,
East China Normal
University

…21

14:40

Coffee break

14:50

Aryl Fluorides: a Versatile Synthetic Platform for
Natural Product Synthesis

15:20

Total Synthesis of Bioactive
Efficiency and Diversity

15:50

NaturalCoffee break

16:00

Development of Chemical Assembly Lines Generating Hiroki Oguri,
Skeletally Diverse Natural Products and Their Variants Tokyo Univ. of Agriculture
and Technology

16:30

Complex Natural Product as a Driving Force for
Discovery in Organic Synthesis and Chemical Biology

Xiaoguang Lei,
Peking University

…25

17:00

Closing Remarks

Representative from CCS
Biao Yu
Shanghai Institute ofOrganic Chemistry

…13

…23

1

7th CCS/CSJ Younng Chemists ForumF

Wellcome AddresA
ss
Dearr Friends annd Colleaguues:
On behalf of the ChineseC
chem
mists attend
ding the 7th
h CCS (TheChine
ese Chemicall Society)‐CSJJ (The Chemical Society ofo Japan) Joint Forum, I
expre
ess my sincere gratitude to our Japaanese colleag
gues for hostting such awond
derful event in the beautiiful campus ofo Keio Unive
ersity.
fon the Frontierr in Organicc Synthesis
This yeaar’s forum focuses
toward Middle Molecular
M
Strrategy. Therrefore, peptides, carbohyydrates, aswell as the diverrse natural products,pcoovering the core space of organic
molecules will bee the topics.. Chemical syynthesis to deliver thesee molecules and to makke thecorreesponding prrobes for deeciphering their function
ns have alw
ways been th
he major tassks oforgan
nic chemists; the young colleagues formfChina anda Japan will
w enjoy excchanging thee newvisionns and new discovery.
dcandd changing world,w
deliveery of usefu
ul molecules and exchan
nge ofIn this complex
viewss face to facee are two mo
ost valuable measuresm
to make the would better.
I believee all the participants will enjoy the chhemistry we bringb
togethher, and the cherrycblosssom season asa well. And I wish this billateral Forumm for young chemistscwilll continue forever.

Proffessor Biaao Yu
State Key Laboraatory of Bio-oorganic and NaturalN
Prod
ducts Chemisstry, Shanghaai Institute ofOrgannic Chemistrry, CAS
345 Lingling
L
Roaad, Shanghai 200032, China
Tel & Fax: (+86)--21-549251331
E-m
mail: byu@sioc.ac.cn

Education
nal Backgroound1989 B.Sc., Depaartment of Tecchnical Physiics, Peking University
U
CCA
AS (supervissor: Prof. Yonngzheng Hui)
1995 Ph D., Shannghai Institutee of Organic Chemistry,Profession
nal Career

1995 New York University
U
(PD
D)
C
1996 Assistant prrofessor, Shannghai Institutee of Organic Chemistry, CAS
C1997 Associate prrofessor, Shannghai Institutte of Organic Chemistry, CASy, CAS
1999 Professor, Shanghai Instiitute of Organnic Chemistry

Research Interests
I

Total synthessis, synthetic methodologyy, and chemiccal biology off carbohydrattes andglycooconjugates.

Awards

A number off awards incluuding the Nattional Natural Science Aw
ward (2010), thhe Lilly Scien
ntificExcelllence Award (2012), and Fellow
Fof thee Royal Socieety of Chemiccal (2016).



Recent Publications

1.

Total synthessis of periploside A, a uniquue pregnane hexasaccharidehe with potent immunosupprressive
effects. Zhang, X.; Zhou, Y.;
Y Zuo, J.; Yuu, B. Nature Commun.
C20155, 6: 5879.
A
Nie, S.;
S Li, W.; Yu,, B. J. Am. Chhem. Soc. 2014
4, 136,
Total synthessis of nucleosiide antibiotic A201A.
4157-4160.
Mechanistic insights into the gold(I)-catalyzed activ
vation of glyccosyl ortho-allkynylbenzoattes forglycosidationn. Tang, Y.; Li, J.; Zhu, Y.; Li,
L Y.; Yu, B. J.
J Am. Chem. Soc. 2013, 1335, 18396-184
405.
Assembly of naturally occuurring glycosiides, evolved tactics and glycosylation mmethods. Yu, B.;
B Sun,
J.; Yang, X. Acc.
A Chem. Rees. 2012, 45, 1227-1236.
1

2.
3.
4.

FRONTIER IN ORGANIC SYYNTHESIS TOWWARD MIDDLLE MOLECULAAR STRATEGY
Y

Koicchi Fukasse
Profeessor
Gradduate Schoool of Sciencee, Osaka Unniversity
Addrress: Machikaneyama 1-1,
1 Toyonaaka, Osaka, 560-0043, JapanJ
Tel: (+81)(
6-68550-5388
FAX
X: (+81) 6-68850-5419
E-maail: koichi@@chem.sci.oosaka-u.ac.jpp
 Education
nal Backgroound
19822 B.Sci., Ossaka Univerrsity (supervvisor: Prof. Tetsuo Shibba)
19877 Doctor off Science, Graduate
G
Schhool of Scieence, Osakaa Universityy (supervisor: Prof.
Tetsuo Shhiba)
 Profession
nal Career
19877 Research Fellow
Fof Jaapan Society for the Prromotion off Science, O
Osaka Univeersity
19888 Research Associate,A
G
Graduate
Scchool of Science, Osakaa Universityy
19944-1995 Postddoctoral Fellow, Deparrtment of Ch
hemistry, Columbia
C
Unniversity (Professor W..
Clark Still)
19966 Assistant Professor,
P
G
Graduate
Schhool of Scieence, Osakaa Universityy
19988 Associate professor,pG
Graduate
Scchool of Science, Osakaa Universityy
20044 Professor, Graduate School
Sof Sccience, Osakka Universiity
 Research Fields
F
Orgaanic synthessis, Natural product cheemistry, Biooorganic cheemistry, Chhemical biology,
Carbbohydrate chhemistry, Innnate immunnity, Combiinatorial cheemistry, Moolecular imaaging.
 Awards
19944 The Chem
mical Societty of Japan AwardA
For Young
Y
Chem
mists
20033 BCSJ awaard (the besst paper awaard of Bull. Chem. Soc. Jpn., Vol 776. March)
20088 BCSJ awaard (the besst paper awaard of Bull. Chem. Soc. Jpn., Vol 881. July)
20099 Dohgane Award,A
whiich is given to a researccher who mademsignificcant contrib
bution to theefield of auutomated floow and miccroreactor (GGroup for ResearchR
on Automatedd Flow andMicroreacctor Synthessis, Kinki ChemicalCSo
ociety, Japann)2011 The Chem
mical Societty of Japan AwardA
for Creative
C
Woork


Recent Publications

1. "S
Synthesis of peptidoglycaan fragmentss from Enteerococcus faaecalis with Fmoc-strateg
gy for glycaan
eloongation", N.. Wang, H. Hasegawa,
H
CYY. Huang, K.. Fukase, andd Y. Fujimotoo, Chem. Asia
an J. 2017, 12,277-30.
2. "CChemical syntthesis of a coomplex-type N-glycanN
conntaining a corre fucose", M
M. Nagasaki, Y.
Y Manabe, N.
NMMinamoto,
K. Tanaka,T
S. Sillipo, S. Molinnaro, and K. Fukase,F
J. Orgg. Chem. 20166, 81, 10600--10616.
3. “A
A reduction-bbased sensor forf acrolein conjugatescwithw the inexppensive nitrobbenzene as ann alternative to
moonoclonal anttibody” M. Taakamatsu, K. Fukase, R. Oka,O S. Kitazuume, N. Tanigguchi, and K. Tanaka K. Scci.
Reep. 2016, 6, 355872.
4. "E
Efficient synthesis of the disiallylated tetraasaccharide motif in N-glycans through anaammide-protectiion strategy."" J. Zhou, Y.. Manabe, K. Tanaka, and K. Fukase,, Chem. Asia
an J. 2016, 11,14436-1440.

2

3

7th
h CCS/CSJ You
ung Chemistss Forum

Junichiro Yamaguchi
Assoociate Profeessor
Facuulty of Sciennce and Enggineering, Waseda
W
Univversity
3-4-11 Ohkubo, Shinjuku,
S
Tookyo 169-8555, Japan
Phonne: +81-3-52286-3225
E-maail: junyamaaguchi@waaseda.jp
 Education
nal Backgroound20022 B.Sc. Tokyyo Universiity of Sciencce, Japan (ssupervisor: Prof.
P
YujirooHayashi)20044 M.Sc. Graduate
G
Scchool of EngineeringEg, Tokyo University of Sciencce, Japan(supervisoor: Prof. Yujjiro Hayashhi)
20066 Exchange Student, Thhe Scripps ResearchR
Institute, USA
A (Prof. K. C
C. Nicolaouu)20077 Doctor of Engineerinng, Graduatee School off Engineerinng, Tokyo U
University of Science,
Japan (suppervisor: Prrof. Yujiro Hayashi)H Profession
nal Career
20077 Postdoctooral Researccher, The Sccripps Research Instituute, USA (wwith Professor. Phil S.
Baran)
20088 Assistant Professor, Graduate
G
Scchool of Sciience, Nagooya Universsity, Japan(with Proffessor Kenichiro Itami))
20122 Associatee Professor, Graduate School of Sccience, Nagooya Universsity, Japan
20166 Associate Professor (PI), Faculty of Scieence and Enngineering, Waseda University,
UJapan Research Interests
I1) Organic synnthesis
2) Synthesis ofo natural prroducts
 Awards
C
20099 Teijin Phaarma Awardd in Synthetic Organic Chemistry,Japan
2011 Young Scientist’s Research Awaard in Natural Product Chemistry,C
JJapan20122 The Chem
mical Societty of Japan LectureL
Awward for Youung Chemistts
20133 Japan Uniion of Chem
mical Sciencce and Techhnology Cheemistry Com
mmunicatio
on Award
20133 The Chem
mical Societty of Japan AwardA
for Distinguishe
D
ed Young C
Chemists
20144 Banyu Chhemist Awarrd
20144 Thieme ChemistryC
Joournal Awarrd
20144 Asian Corre Lectureshhip Award, China and ThailandT

Recent Publications

1. “T
Toward an Ideal
I
Syntheesis of (Bio))molecules throught
Direect Arene A
Assembling Reactions”
R(A
Accounts), Yaamaguchi, J.; Itami, K. Bull.
B
Chem. Soc.
S Jpn. 20117 DOI: 10.1246/bcsj.201
160365.
2. “D
Decarbonylattive Organobboron Cross-coupling of Eters by Nckkel Catalysiss” Muto K.; Yamguchi,YJ.;; Musaev, D. G.; Itami, K.
K Nature. Coommun. 2015
5, 6, 7508.
3. “S
Synthesis andd Characteriization of Hexaarylbenz
Hzenes with FiveF
or Six Different Substituents
Ennabled by Prrogrammed Synthesis”, Suzuki, S.; Segawa, Y.; Itami, K.; Yamaguchi,, J. Nature
Chhem. 2015, 7,
7 227.
4. “C
Concise Synttheses of Dicctyodendrins A and F by a Sequentiaal C−H Functtionalizationn Strategy”,
Yaamaguchi, A.;
A Chepiga, K.;
K Yamaguuchi, J.; Itamii, K.; Daviess, H. J. Am. Chem. Soc. 2015, 137,
6444.

FRONTIER IN ORGANIC SYNTHESIS TOWARD MIDDLE MOLECULAR STRATEGY

Aromatic Molecules:
Decarbonylative Coupling and Multiple Arylation
Junichiro Yamaguchi
Department of Applied Chemistry, Waseda University,
3-4-1 Ohkubo, Shinjuku, Tokyo 169-8555, Japan
In recent years, catalytic decarbonylative coupling reactions using aromatic esters
as aryl electrophiles have been studied to produce various transformations. We report
the development of catalytic decarbonylative transformations of aromatic esters, which
are C–H arylation of azoles, Suzuki–Miyaura coupling, alkynylation, andintramolecular etherifications under the influence of Pd or Ni catalysts. The key forthese achievements was newly developed catalytic systems in which our unique ligand
was employed (Figure 1A). By utilization of these reactions, we successfully achieved
applications such as the formal synthesis of naturally occurring compounds.
Meanwhile, multiply arylated aromatics have often been found in natural products,
pharmaceuticals and functional organic materials. We achieved the programmed
synthesis of multiply arylated aromatics using sequential C–H couplings, crosscouplings, and Diels–Alder reaction of thiophene S-oxides. This synthetic method canprovide hexaarylbenzenes, pentaarylpyridines, multiply arylated naphthalenes, and amultiply arylated anthracene bearing different aryl groups (Figure 1B).
I would like to talk about above two topics about transformation of aromatic
molecules in this symposium.

Figure 1.

4

5

7th
h CCS/CSJ You
ung Chemistss Forum

Gonng ChenProfeessor of Cheemistry
Statee Key Laborratory of Elemento-Orgganic Chem
mistryNankkai Universiity
Addrress: Weijinn Rd 94, Tiaanjin 3000711, China
Tel & Fax: (+866)-22-8366-22300
E-maail: gongcheen@nankai..edu.cn
 Education
nal Backgroound
19988 B.Sc., Nannjing Univeersity
20044 Ph.D., Deepartment off Chemistryy, Columbiaa Universityy (supervisor: Prof. Dallibor
Sames)
 Profession
nal Career
20055 Memoriall Sloan-Ketttering Canccer Center (PPostdoc)
20088 Assistant professor, The
T Pennsyllvania Statee Universityy
20144 Associatee professor, The Pennsyylvania Statee Universityy
20155 Professor,, Nankai Unniversity
 Research Interests
I1) Syynthesis of complexcpeeptides and carbohydratctes2) C--H Functionnalization
 Awards
2011 National ScienceS
Fouundation CA
AREER Aw
ward
20133 Amgen Young
Yo
Investtigator
20166 WuXi ApppTec Scholaar Award inn Life Scien
nce and Chem
mistry

Recent Publications

1. "T
Total Synthessis of Celoggentin C via Stereoselecttive C−H Activation", Y
Yiqing Feng and Gong
Chhen. Angew. Chem., Int. Ed.
E 2010, 499, 958-961.
2. "S
Syntheses and Transformmations of --Amino Acid
ds via Palladdium-Catalyzzed Auxiliarry-Directed3
spp C−H Funcctionalizationn", Gang He, Bo Wang, William A Nack,N
and G
Gong Chen. Acc.
A Chem.
Rees. 2016, 49, 635-645.
3. "B
Benzazetidinee Synthesis via Palladiuum-Catalyzed
d Intramoleccular C−H A
Amination ", Gang He,
Gaang Lu, Zhenngwei Guo, PengP
Liu, annd Gong Chen. Nature Chhem. 2016, 88, 1131-1136.
4. "T
Total Synthessis of Mannoopeptimycinss  and ", Bo
B Wang, Yuunpeng Liu, Rui Jiao, Yiiqing Feng,
Qiiong Li, Chen Chen, Loong Liu, Gaang He, andd Gong Cheen. J. Am. C
Chem. Soc. 2016,
2
138,39926-3932.

FRONTIER IN ORGANIC SYNTHESIS TOWARD MIDDLE MOLECULAR STRATEGY6

C－H Functionalization Strategy for Chemical Synthesis of
-Amino Acids and Complex Peptides
Gong Chen
State Key Laboratory of Elemento-Organic Chemistry, Nankai University,
Tianjin, 300071, P. R. China
-Amino acids (AA) are one of the most useful chiral building blocks for synthesis. Despite
significant advances in synthetic methodology, the efficient synthesis of enantiopure AAs carrying
complex side chains, as seen in numerous peptide natural products, remains challenging.
Complementary to the conventional synthetic strategies, a strategy based on the selectivefunctionalization of side chain C−H bonds, particularly sp3 hybridized C−H bonds, of various readily
available AA precursors may provide a more straightforward and broadly applicable means for thesynthesis and transformation of AAs. Over the past few years, we have carried out systematicinvestigation of palladium-catalyzed bidentate auxiliary-directed C−H functionalization reactions forAA substrates. Our strategies utilize two different types of amide-linked auxiliary groups, attachedat the N or C terminus of AA substrates, to exert complimentary regio- and stereo-control on C−Hfunctionalization reactions through palladacycle intermediates. A variety of AA precursors canundergo multiple modes of C(sp3)−H functionalization, including arylation, alkenylation,
alkynylation, alkylation, alkoxylation and intramolecular aminations, at the ,  and even  positions
to form new AA products with diverse structures. In addition to transforming AAs at previously
unreachable positions, these palladium-catalyzed C−H functionalization strategies enable new
retrosynthetic logic for the synthesis of many basic AAs from a common alanine precursor. Thisapproach reduces the synthetic difficulty for many AAs by bypassing the requirement forstereocontrol at C, and relies on straightforward and convergent single-bond couplingtransformations at the -methyl position of alanine to access a wide range of -mono-substituted
AAs. Moreover, these -mono-substituted AAs can undergo further C−H functionalization at the-methylene position to generate various -branched AAs in a stereoselective and programmable
fashion. These new strategies offer readily applicable methods for synthesis of challenging AAs
and facilitate the efficient total synthesis of complex peptide natural products.

CHF: CH functionalization

R''
H

R
H

H

CHF
R

H 2N

CO 2H

H 2N

Ala

H

CHF

H 2N

R'''

R

CO 2H

H 2N

CHF
R'

H

CO 2H

R'

CO 2H
R

R'

N

CO 2H

R
R
H 2N

easily accessible
AA precursors

R''

H
CO 2H

N

H 2N
O

complex AAs
and derivatives

H

H

7

7th
h CCS/CSJ You
ung Chemistss ForumYokko Saikaw
wa
Assoociate Professor
Depaartment of AppliedA
Cheemistry, Facculty of Scieence and Teechnology,
Keioo Universityy
Addrress: 3-14-11 Hiyoshi, Kohoku-ku,
KYokohama 223-8522, Japan
Tel & Fax: (+81)-45-566-1562
E-maail: saikawaa@applc.keiio.ac.jp
 Education
nal Backgroound19998 B.Sc., Keio
K University (superrvisor: Prof.. Masaya NA
AKATA)
20000 M.Sc., Graduate School
Sof Sccience and Technology,
T, Keio Univversity (supeervisor:
Prof. Masaya
M
NAK
KATA)
20004 Doctor of Science,, Graduate School
Sof Science and Technologyy, Keio Univ
versity(supervvisor: Prof. Masaya
M
NA
AKATA)
 Profession
nal Career
20002 Researcch Assistantt, Keio Univversity
20007 Assistaant Professoor, Keio Uniiversity
20008 Visitingg Scholar, Harvard
H
Medical Schoool (~2009, with
w Prof. Joon Clardy)
20114 Associaate Professoor, Keio Unniversity
 Research InterestsI1)
Total syynthesis of natural prodducts
2)
Isolatioon and struccture determ
mination of bioactivebnaatural produucts
 Awards
20003 Incentivve Award of 45th Sympposium on thet Chemisttry of Naturral Productss
20114 CSJ Aw
ward for Ouutstanding YoungY
Womeen Chemists


Recent Publications
1.

2.

3.

4.

“Syntheesis and Bioological Evaaluation of KendomycinKn and Its Annalogues” Tanaka,
T
K.;
Matsuyaama, H.; Waatanabe, M.; Fujimori, Y.;
Y Ishibashi, K.; Ozawa, T.; Sato, T..; Saikawa,Y.; Nakata. M. J. Orrg. Chem. 20014, 79, 9922
29947.
Isopropyl“Smootthfrom
Isoinddolinone
Formation
Carbamaates
via
Bischlerr-Napieralskki-type Cycliizaion” Adaachi, S.; Onoozuka, M.; Yoshida, Y..; Ide, M.;
Saikawaa, Y.; Nakataa, M. Org. Leett. 2014, 16,, 358.
“Total SynthesesS
off Lactonamyccin and Lactoonamycin Z with Late-Sttage A-Ring Formation
and Glyycosylation”” Adachi, S.;
S Watanabee, K.; Iwataa, Y.; Kameeda, S.; Miyaoka, Y.;
Onozukka, M.; Mitssui, R.; Saikkawa, Y.; Nakata,N
M. Angew.
A
Chemm., Int. Ed. 2013, 52,20872091.
S
off Kendomyciin Featuring Intramolecuular Dötz Beenzannulationn” Tanaka,“Total Synthesis
K.; Wattanabe, M.; Matsuyama,Mhi, K.; Saikaw
wa, Y.; Nakaata. M. Org. Lett.
L
2010,
H.; Ishibash
12, 17000.

FRONTIER IN ORGANIC SYNTHESIS TOWARD MIDDLE MOLECULAR STRATEGY

Synthesis and Biological Evaluation of Antibiotic Polyketides
Yoko Saikawa
Department of Applied Chemistry, Faculty of Science and Technology, Keio University
3-14-1 Hiyoshi, Kohoku-ku, Yokohama 223-8522, Japan
There are a variety of polyketides with complex structure and fascinating
bioactivities. We are focusing on the synthesis of such attractive natural products todevelop new strategy useful for their syntheses and to reveal the substructure requisite
for their bioactivities.
Ansa-type antibiotic kendomycin (1) has a unique quinone methide architecture
connected to a highly-substituted tetrahydropyran ring and possesses potent
antibacterial and cytotoxic activities. 1 was synthesized via intramolecular Dötz
reaction which enabled simultaneous aromatization and macrocyclization. Using thisefficient method to construct an ansa-skeleton, new ansa-type analogs were alsosynthesized. Antimicrobial activities of the analogs revealed necessity of theansa-skeleton.
On the other hand, total synthesis of lactonamycin (2), a potent antimicrobial
polyketide, was performed via sequential construction of its six rings followed byglycosylation. In the course of the synthesis, we developed a new method forconstruction of isoindolinone moiety (A-ring), that is modified Bischler-Napieralski
reaction. Various model compounds and synthetic intermediates of 2 provided insight
into the biological function of its complex structure which is dug down to the individual
factors such as -lactam (A-ring), EF-ring configuration, and the rhodinose linkage.
The latest topic of a cytotoxic naphthofuranoxepin dioscorealide A (3) consists of
its intriguing structural feature and investigation of its asymmetric synthesis via chiraltranscription of the synthetic intermediate into 3 with mobile chiral center.

8

9

7th
h CCS/CSJ You
ung Chemistss ForumWen
njun Tangg
Reseearch Professsor
Statee Key Laborratory of Biio-Organic & Natural Products
P
Chhemistry
Shannghai Instituute of Organnic Chemisttry, Chinesee Academy ofo Sciences
345 Ling
L
Ling Road,R
Shangghai 2000322
Tel: (+0086)-21(-54925515
E-maail: tangwennjun@sioc.aac.cn
 Education
nal Backgroound
19955 B.Eng., East Chinna Universsity of Scciences andd Technology(supervisoor: Prof. Guuohou Chenng)
19988 M.Sc., Shhanghai Insttitute of Orgganic Chem
mistry, CAS (supervisor(: Prof. Daw
wei Ma)20033 Ph.D., Deepartment ofo Chemistryy, The Pennnsylvania StateS
Univerrsity (supervvisor: Prof..
Xumu Zhhang) Profession
nal Career
20033 Postdoctooral fellow, The
T Scrippss Research InstituteI(suupervisor: P
Prof. KC Niccolaou)
20055 Senior sciientist, Chem
mical Deveelopment, Boehringer Inngelheim Phharmaceuticcals Inc.
20099 Principal scientist, Chhemical Deevelopment,, Boehringer Ingelheimm Pharmaceu
uticals Inc.
2011 Research professor, Shanghai Institute off Organic Chemistry,C
Chinese Academy
A
off
Sciences Research Interests
I1) Deesign and developmentdt of novel, efficient,eannd practical chiral catalyytic reactionns;2) Tootal synthesis of compllex and biologically acttive natural products;
 Awards
20122 National “Thousand“
Talents” Yoouth programm20122 Thieme ChemistryC
Joournal Awarrd
20155 Asian Corre Lectureshhip Award
20155 National HomogenouH
us Catalysiss Youth Awaard


Recent Publications

1. “T
Transition-Metal-Free Steereospecific Cross-Couplling with Alkkenylboronicc Acids as Nu
ucleophiles””
Lii, C.; Zhang, Y.; Sun, Q.; Gu, T.; Pengg, H.; Tang, W.*
W J. Am. Chem.
C
Soc. 20016, 138, 10
0774.
2. “S
Synthesis of Chiral 1,4-B
Benzodioxannes and Chroomans by Ennantioselectiive Palladium
m-Catalyzedd
Allkene Aryloxxyarylation Reactions”
R
H N.; Li, K.;Hu,
K Wang, Z..; Tang, W.* Angew. Cheem., Int. Ed.
20016, 55, 50444
3. “H
Highly Enanntioselective Rhodium-C
Catalyzed AdditionAof Arylboroxinnes to Simp
ple Ketones::
Effficient Synthhesis of Esciitalopram” Huang,H
L.; Zhhu, J.; Jiao, G.; Wang, Z
Z.; Yu, X.; Deng,
D
W.-P.;**Taang, W.* Anggew. Chem., Int.
I Ed. 20166, 55, 4527.
4. "S
Synthesis off Chiral α-A
Amino Tertiaary Boronicc Esters by Enantioseleective hydrooboration off
α-Arylnamidess", A Hu, N.; Zhao, G.; Zhang,Z
Y.; Liiu, X.; Li, G.; Tang, W*... J. Am. Chem
m. Soc. 20155,
1337, 6746.
5. “E
Enantioselecttive Palladium-Catalyzeed Dearomaative Cyclizzation for Efficient Synthesis
S
off
Teerpenes and Steroids”
S
Duu, K.; Guo, P.;
P Chen, Y.; Cao, Z.; Wanng, Z,; Tang, W* Angew
w. Chem., Int.
Edd. 2015, 54, 3033.
3

FRONTIER IN ORGANIC SYNTHESIS TOWARD MIDDLE MOLECULAR STRATEGY

Natural Product Synthesis Facilitated by Ligand Design
Wenjun Tang
State Key Laboratory of Bio-Organic & Natural Products Chemistry, Shanghai Instituteof Organic Chemistry, Shanghai 200032, P.R.China

The asymmetric intramolecular Heck reaction have become one of most successful
method for constructing polycyclic skeletons bearing an all-carbon chiral quaternary
center in natural product synthesis. Despite its versatile synthetic utilities, theasymmetric Heck cyclization employs an olefinic starting material which often requires
multiple synthetic steps to prepare. In addition, the transformation of its olefinic productto a target molecule is sometimes tedious. An attractive alternative is enantioselective
intramolecular dearomative cyclization which employs an often more accessible
substrate with an aryl moiety and leads to a multicyclic product bearing an all-carbon
quaternary center. Because of the closer resemblance of the cyclic product to a varietyof chiral natural products, this method offers advantages over the Heck reaction for thesynthesis of a number of chiral polycyclic natural products. The key issue is how toachieve satisfactory reactivity, chemoselectivity, and enantioselectivity by employing aneffective chiral ligand. Herein we described the ligand design that have enabled aneffective dearomative cyclization and the efficient asymmetric synthesis of several
biologically important alkaloids and polyketides.

Figure 1.

Polycyclic natural products

10

11

7th
h CCS/CSJ You
ung Chemistss Forum

Go Hirai
H
Profeessor
Gradduate Schoool of Pharmaaceutical Scciences, Kyu
ushu Univerrsity
Addrress: 3-1-1 Maidashi,
M
H
Higashi-ku,
Fukuoka 81
12-8582, Jaapan
Tel & Fax: (+81)-92-642-6603
E-maail: gohirai@@phar.kyushu-u.ac.jp
 Education
nal Backgroound19977 B.Sc., Tohhoku Univeersity (superrvisor: Prof.. Masahiro Hirama)H
19999 M.Sc., Grraduate School of Sciennce, Tohoku
u Universityy (supervisoor:
Prof. Massahiro Hiramma)
20022 Doctor off Science, Graduate
G
Schhool of Scieence, Tohokku Universitty (supervissor: Prof.
Masahiro Hirama) Profession
nal Career
20022 Assistant professor, InstituteIof Multidiscip
M
plinary Reseearch for Addvanced Maaterials,
Tohoku UniversityU(ssupervisor: Prof. Mikik
ko Sodeoka))
20044 Research Scientist, Synthetic
S
Orrganic Chem
mistry Labooratory, RIK
KEN (supervvisor: Prof.
Mikiko Soodeoka)
20100 Senior Reesearch Scieentist, Synthhetic Organiic Chemistrry Laboratorry, RIKEN(supervisoor: Prof. Miikiko Sodeooka)
20166 Professor,, Graduate School
Sof Pharmaceutical Sciences, Kyushu U
University
 Research InterestsI1) Crreation of bioactive moolecules witth unique fu
unctions
2) Deevelopmentt of useful molecularmtoools for undderstanding glycoconjuggates functiions
 Awards
20100 Central GlassG
Award in Synthetiic Organic Chemistry,
C
J
Japan
20100 Incentive Award in thhe Pharmaceutical Sociiety of Japaan Kanto Brranch
20100 Asian Corre Program Lectureshipp Award fro
om Thailandd
20144 Incentive Award in Synthetic
S
Orrganic Chem
mistry, Japann
20144 Incentive Award 20144 in GlyoTookyo, Japann20155 Thieme ChemistryC
Joournal Awarrd 2015


Recent Publications

1.

Photochemiical and Additive-FreeA
e Coupling Reaction of α-Cumyyl α-Keto Esters viaa
Intermolecuular C–H Boond Activatioon, Eisuke Ota,O Yu Mikkame, Go Hiirai, Shigeru
u Nishiyama,,
Mikiko Soddeoka. SYNLE
ETT 2016, 266, 1128-1132
2.
Contributionn of Cage-Shaped Struccture of Physsalins to Theeir Mode off Action in Inhibition
I
off
NF-kB Actiion, Masaakii Ozawa, Maasaki Morita, Go Hirai, Satoru Tamurra, Masao Kaawai, Ayakoo
Tsuchiya, KanaK
Oonumma, Keiji Marruoka, and Mikiko
M
Sodeooka. ACS M
Med. Chem. Lett.
L
2013, 4,,730-735.
Kinetically Controlled One-Pot Foormation of DEFGH-Riings of Typpe B Physallins throughh
Domino-Typpe Transformmations, Maasaki Morita, Go Hirai, Meguni Ohkkubo Hiroyu
uki Koshino,,
Daisuke Hasshizume, Keeiji Maruoka,, and Mikiko
o Sodeoka. Org.
O Lett. 20112, 14, 3434--3437.

2.

3.

FRONTIER IN ORGANIC SYNTHESIS TOWARD MIDDLE MOLECULAR STRATEGY

Synthesis of Monomers for Spectomycin B1,
A Middle Size SUMOylation Inhibitor Molecule
Go Hirai,a,b Yusaku Nomura,b Frederic Thuaud,b Daisuke Sekine,b and Mikiko SodeokabaGraduate School of Pharmaceutical Sciences, Kyushu University, 3-1-1 Maidashi,
Higashi-ku, Fukuoka 812-8582, Japanb
RIKEN, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan
Spectomycin B1 (SMB1) was isolated from streptomyces spectabilis in 1994, andits monomeric homolog, spectomycin A1 (SMA1) and A2 (SMA2), were also identified
at the same time.1 Our collaborators Dr. It and Dr. Yoshida recently reported that SMB1
exhibited the inhibitory activity for protein SUMOylation, through direct binding to
SUMO-conjugating enzyme E2.2
Protein SUMOylation is one of the post-translational modification, in which lysine
residue on substrate protein is modified by small ubiquitin-like modifier (SUMO).
Dysregulation of SUMOylation pathway is involved in several diseases, andupregulation of enzymes related to SUMOylation was observed in several cancers. Thus,
SUMOylation inhibitors would be useful as tools to understand the precise role of
SUMOylation as well as candidates for therapeutic agents.
Although the dimeric structure was shown to be requisite for its anti-microbialactivity,1 the effect of SMAs for protein SUMOylation has not been clarified yet due tothe unavailability of materials. Furthermore, relative and absolute stereochemistry of
SMAs and SMB1 remains to be determined. This time, we synthesized all possible
stereoisomers of SMA1 and SMA2, in order to confirm their absolute structures as wellas the importance of dimeric structure of SMB1 on inhibitory activity for protein
SUMOylation.
We would like to thank Ms. Satoko Maeda, Dr. Akihiro Ito, and Prof. Minoru
Yoshida for conducting biochemical experiments. We also thank Dr. Hiroyuki Koshino
for NMR measurement, Dr. Daisuke Hashizume for X-ray crystallographic analysis, and
Mr. Thomas Cruchter for his kind support.

Figure 1.

Structures of SMB1, SMA1, and SMA2

References
1. Staley, A. L.; Rinehart, K. L. J. Antibiot. 1994, 47, 1425-1433.
2. Hirohama, M.; Kumar, A.; Fukuda, I.; Matsuoka, S.; Igarashi, Y.; Saitoh, H.; Takagi, M.;
Shin-ya, K.; Honda, K.; Kondoh, Y.; Saito, T.; Nakao, Y.; Osada, H.; Zhang, K. Y.; Yoshida, M.;
Ito, A. ACS Chem. Biol. 2013, 8, 2635-2642.

12

13

7th CCS/CSJ Young Chemists Forum

Qian Wan
Professor of Chemistry
School of Pharmacy, Huazhong University of Science andTechnology
Address: Hangkong Road 13, Wuhan, Hubei, China
Tel & Fax: (+86)-13971060097
E-mail: wanqian@hust.edu.cn
 Educational Background1997 B.Sc., Central China Normal University
1999 M.Sc., Paris-Sud (XI) University (supervisor: Prof. Claudine Augé)
2004 Ph.D., Paris-Sud (XI) University (supervisor: Prof. André Lubineau) Professional Career2004 Research Fellow, Memorial Sloan-Kettering Cancer Center, New York, NY, USA(Advisor: Prof. Samuel J. Danishefsky)2007 Scientist, Department of Medicinal Chemistry, Amgen Inc., Cambridge, MA, USA
2012 Professor, School of Pharmacy, Huazhong University of Science and Technology
2014 Vice Dean of School of Pharmacy
 Research Interests
1) Carbohydrate Chemistry2) Free Radical Chemistry Awards
2017 Asian Core Program Lectureship Award (to Taiwan)
2017 Asian Core Program Lectureship Award (to Singapore)2015 7th Asian Community of Glycoscience and Glycotechnology Conference Best Poster
Award, Miyagi, Japan
2012 “Thousand Talents Program” Young Investigator Award
2011 Amgen First Green Chemistry in Medicinal Chemistry Award

Recent Publications

1. "Remote Activation of Disarmed Thioglycosides in Latent-Active Glycosylation via Interrupted
Pummerer Reaction", Xiao, X.; Zhao, Y.; Shu, P.; Zhao, X.; Liu, Y.; Sun, J.; Zhang, Q.; Zeng, J.; Wan,
Q.* J. Am. Chem. Soc. 2016, 138, 13402.
2. "Glycosylation via Remote Activation of Anomeric Leaving Groups: Development of
2-(2-Propylsulfinyl)benzyl Glycosides as Novel Glycosyl Donors", Org. Chem. Front. 2016, 3, 177.
3. "Interrupted Pummerer Reaction in Latent-Active Glycosylation: A Novel Type of Glycosyl Donors
with Recyclable and Regenerative Leaving Group", Angew. Chem. Int. Ed. 2015, 54, 14432.
4. "Selective S-deacetylation Inspired by Native Chemical Ligation: Practical Syntheses of Glycosyl
Thiols and Drug Mercapto-analogues", Shu, P.; Zeng, J.; Tao, J.; Zhao, Y.; Yao, G.; Wan, Q.* Green
Chem. 2015, 17, 2545.
5. "Stereoselective Synthesis of α-linked 2-Deoxy Glycosides Enabled by Visible Light MediatedReductive Deiodination", Wang, H.; Tao, J.; Cai, X.; Chen, W.; Zhao, Y.; Xu, Y.; Yao, W.; Zeng, J.; Wan,
Q.* Chem. Eur. J. 2014, 20, 17319.

FRONTIER IN ORGANIC SYNTHESIS TOWARD MIDDLE MOLECULAR STRATEGY

Remote Activation of O/S-Benzyl Glycosides
in Latent-Active Glycosylation
Xiong Xiao, Yueqi Zhao, Yang Xu, Jianchang Sun, Jing Fang, Xiang Zhao, Yan Liu,
Lingkui Meng, Jing Zeng and Qian Wan*
School of Pharmacy, Huazhong University of Science and Technology,
Wuhan, Hubei, P. R. China

Latent O/S-glycosides, O/S-2-(2-propylthiol)benzyl (PTB) glycosides, wereconverted
intothecorresponding
activeglycosyl
donors,O/S-2-(2-propylsulfinyl)benzyl (PSB) glycosides, by a simple and efficient oxidation.
Treatment of PSB donors and various acceptors with triflic anhydride provided thedesired glycosides in good to excellent yields. Three natural hepatoprotective glycosides,
Leonuriside B, Leonoside E and F, were synthesized efficiently in a convergent [3+1]manner with this newly developed methods. The total syntheses also led to structuralrevisions of these phenylethanoid glycosides.

Figure 1.

Interrupted Pummerer reaction mediated glycosylation

14

15

7th
h CCS/CSJ You
ung Chemists ForumYoshhiyuki Manabe
Assisstant Professsor of Chem
mistryDepaartment of Chemistry,C
G
Graduate
Scchool of Sciience, Osakka Universitty
Addrress: 1-1 Maachikaneyam
ma, Toyonaaka, Osaka 560-0043,
5
J
Japan
Tel & Fax: (+81)-6-6850-5391
E-maail: manabey12@chem
m.sci.osaka-uu.ac.jp
 Education
nal Backgroound20066 B.Sc., Facculty of Scieence, Tohokku Universiity, (superviisor: Prof.
Minoru Ueda)
U
20088 M.Sc., Grraduate School of Sciennce, Tohoku
u Universityy (supervisoor: Prof. Min
noru
Ueda)
2011 Doctor off Science, Graduate
G
Schhool of Scieence, Tohokku Universitty (supervissor: Prof.
Minoru Ued)U
 Profession
nal Career
2011 Postdoctraal fellow, Kyushu
K
Univversity
20122 Assistant professor, OsakaO
Univversity
 Research Interests
I1) Naatural produuct
2) Gllycosciencee
3) Chhemical bioology
4) Orrganic synthhesisRecent Publications

1. "C
Chemical Synnthesis of a Complex-Tyype N-Glycan Containingg a Core Fuccose.", Nagaasaki, M.;
M
Manabe,Y.; Minamoto,M
N Tanaka, K.;N.;
K Silipo, A..; Molinaro, A. and Fukaase, K. J. Orrg. Chem.
20016, 81, 106000.
2. "E
Efficient syntthesis of the disialylated tetrasacchariide motif in N-glycan viaa an amide protectionpstrrategy.", Zhoou, J.; Manabbe, Y.; Tanakka, K. and Fu
ukase, K. Chhem. Asian. JJ. 2016, 11, 1436.
1
3. "SSynthesis of the Conjuggates of Tum
mor Antigen
ns with Adjuvants for the Efficien
nt CancerIm
mmunotherappy.", Manabee, Y.; Chang,, T-C.; Li, H-S.;
H
Terao, N.;
N Takamatssu, S.; Tanemmura, M.;M
Miyoshi,E. annd Fukase, K.
K Peptide Sciience 2015, 77.
7
4. "R
Revisiting Brromination ofo C-H Bonnds with Mo
olecular Broomine Usingg a Photo-M
Microflow
Syystem.", Manabe, Y.; Kitawaki,
K
Y..; Nagasaki,, M.; Fukasse, K. Matsuubara, H.: Hino
H
Y.;
Fuukuyama, T. and Ryu, I. Chem.
C
Eur. J.
J 2014, 20, 12750.
5. "E
Efficient Glycosylation
Gn Using In(OTf)3 as a Lewis
L
Acid: Activattion of
N--Phenyltrifluuoroacetimidaate or Thiioglycosides with Haloogenated R
Reagents or PhIO.",
Saalmasan, R. M.; Manabee, Y.; Kitawaaki, Y.; Chaang, T.-C.; Fukase,
F
K. C
Chem. Lett. 2014,
2
43,
9556.

FRO
ONTIER IN ORGANIC SYNTHESIS TOWA
ARD MIDDLEE MOLECULAR
R STRATEGYD
Developm
ment of th
he Novel Cancer
CIm
mmunotheerapy Utiilizing -GGal
Yoshiyuki ManabeYM
andd Koichi Fukkase
Department of Chem
mistry, Gradduate Schoool of Sciencee, Osaka Unniversity, 1--1
Machikakaneyama, Toyonaka,
T
Osaka
O
560-00043, Japann
α--Gal epitoppe (Fig. 1) is a trisacccharide prroduced inmost mammals except in humans. On the otther hand,humanns produce large amouunt of anti-Gal antibod
dies whichinteracct specificcally with the α-gal epitopee. Cancer
immunnotherapy is a prommising theraapy that utilizesuthee
Fig.1 -gal epitopee
patientt’s own imm
mune system
m. Althouggh this theraapy has thepotenttial to treat thet systemicc metastaticc cancer, its applicationns are still liimited becaause of the
weak antigenicityay of tumor antigens.
a
In this study, wew developped novel caancer immun
notherapy
utilizinng the hypeeracute imm
mune response induced by -gal eppitope.
It has alreeady beenreporteed that the expressionof α-galα
on antigens
promootes its upttake owing
to thee interactionn of α-gal
and anti-Galaanntibody toincrease the anti-tumor
immunnoresponsess.1
We
achievved
theefficientsyntheesis of α-gal
αandconjuggation of -gal
withvariouus antigens (Scheme
(
1).
After
the
one-pot
Schemee 1. Synthesiis of -gal annd conjugation with antig
gens.
glycossylationofcompoounds 1, 2 and 3,
obtainned trisacchaaride was coonverted to α-gal succiinimidyl estter 5. Variouus antigens were thenlabeledd with -gaal using 5. We
W also carrried out thee in vivo im
mmunizationn of α-gal conjugatedcantigens. As thee results, productionpof antibodiies was drramatically increased when we
vaccinnated with α-gal
αconjuggated antigeens in comparison to vaaccination w
without α-gaal epitope.
We theerefor succeessfully shoowed that chhemically syynthesized α-gal
αcan bee used as ann adjuvant(additiive to enhannce the imm
mune responnse to the vaaccines) for cancer imm
munotherapyy.2
W also investigatedWe
cancerr immunottherapy
using -gal labeledlcancerr antibody (Fig.
(2).
The caancer cells treatedwith thist-gal labeledlantiboody were killled byhyperaacute rejectiion.
Fig..2. -gal epitoope

Refeennces
1. Tannemura, M., Miyoshi,
ME., Nagano,N
H., Eguchi,E
H., Taniyama,TK.,, Kamiike, W
W., Mori, M., Doki,D
Y.
(20013) Cancer. Sci. 104, 2822-290.

2. Jappan Patent Appplication Noo.2014-263056, Miyoshi, E.,
E Fukase, K.,
K Manabe, Y
Y., Takamatsu,, S.,
Tannemura, M. (2014).

16

17

7th
h CCS/CSJ You
ung Chemists ForumChuuang-Chuuang Li
Reseearch Professsor of Chem
mistrySouthh University ofo Science annd Technologyy of China

Addrress: Southh Universiity of Science andTechnology of China, Shenzzhen 518055, China
Tel & Fax: 86-7555-8801-83333

E-maail: ccli@suustc.edu.cn
 Education
nal Backgroound20011 B.Sc., China Agriculttural University
20066 Ph. D. Pekking Univerrsity (supervvisor: Prof. Zhen Yangg)
20088 Postdoctooral Fellow, The Scrippps Research Institute (suupervisor: P
Prof. Phil S.. Baran) Profession
nal Career
20088 Associatee professor, Peking Uniiversity, Sheenzhen Gradduate Schoool
20144 Research Professor, SouthS
Univeersity of Science and Technology
Tof China Research Interests
I1) Tootal Synthessis of Natural Products2) Deevelopmentt of Novel Synthetic
S
M
Methodologyy Awards
20166 Leading TalentTof Millions of Peeople in Gu
uangdong Prrovince
20155 NSFC Ouutstanding YoungY
Schoolar Award
20144 First-Classs Guangdonng Natural Science Aw
ward
20133 First-Classs Shenzhenn Natural Sccience Awarrd


Recent Publications

1. T
Type II Intram
molecular [5++2] Cycloadddition: Facille Synthesis ofo Highly Fuunctionalizedd Bridged
R
Ring
Systemss. Mei, G.; Liu,
L X.; Qiaoo, C.; Chen, W.; Li, Chuuang-Chuangg* Angew. Chem.
CInt.
E 2015, 544, 1754, doi: 10.1002/aniee.201410806
Ed.,
6.
2. Collective
C
Syynthesis of HumulanolideH
es Using a Metathesis
M
Caascade Reactiion. Han, J.; Li, F.; Li,C
Chuang-Chuaang* J. Am. Chem.
C
Soc., 2014, 136, 13610.
1
3. DearomativeD
Indole [5++2] Cycloadddition Reacctions: Stereeoselective S
Synthesis of Highly
F
Functionalize
ed Cycloheppta[b]indoles. Mei, G.; Yuan,
Y
H.; Gu, Y.; Chen, W.; Chungg, L.; Li,C
Chuang-Chuaang* Angew. Chem. Int. Ed.,E 2014, 53
3, 11051.
1. Stereoselectivee Total Synthheses of (−)--Flueggine A and (+)-Virrosaine B. W
Wei, H.; Qiaoo, C.; Liu,
G..; Yang, Z.*;; Li, Chuang--Chuang Angew.
A
Chem
m. Int. Ed., 20013, 52, 620.

FRONTIER IN ORGANIC SYNTHESIS TOWARD MIDDLE MOLECULAR STRATEGY

Type II Intramolecular [5+2] Cycloaddition
Chuang-Chuang Li*
Department of Chemistry, South University of Science and Technology of China,
Shenzhen 518055, P. R. China

Developing efficient reactions for achieving bridged ring systems is a long-standing
challenge but very significant in organic chemistry, considering that such motif is widely
found in natural products (such as Taxol®) with significant biological activities. So far there
are no general reactions available for the single-step synthesis of bridged
seven-membered-ring systems efficiently. Here, we describe the first type II intramolecular[5+2] cycloaddition reaction,1 which allows the efficient and diastereoselective constructionof various highly functionalized and synthetically challenging bridged seven-membered ringsystems. This simple, thermal transformation has shown a broad substrate scope and is highyielding, with high functional group tolerance and unique endo selectivity. The highly strained
tricyclic cores of ingenol mebutate (Picato®) and cyclocitrinol are synthesized efficiently anddiastereoselectively using this methodology.

Reference
1. (a) Mei, G.; Liu, X.; Qiao, C.; Chen, W.; Li, C.-C. Angew. Chem. Int. Ed. 2015, 54, 1754. (b) Mei, G.; Yuan,
H.; Gu, Y.; Chen, W.; Chung, L.; Li, C.-C. Angew. Chem. Int. Ed. 2014, 53, 11051.

18

19

7th
h CCS/CSJ You
ung Chemistss ForumKenn Ohmori
Assoociate Professor of Cheemistry
Depaartment of Chemistry,C
S
Schoolof Science, Tok
kyo Institutee of Technollogy
Addrress: O-okayyama, Meguuro-ku, Tokkyo 152-855
51, Japan
Tel & Fax: (+81)-3-5734-2761/2788
E-maail: kohmorri@chem.titech.ac.jp
 Education
nal Backgroound19911 B.Sc., Keio Universitty (supervissor: Prof. Sh
hosuke Yammamura)19933 M.Sc., Deepartment ofo Chemistryy, Keio Univ
versity (suppervisor: Proof. S.
Yamamurra)
19966 Doctor off Science, Department
Do Chemistrry, Keio Unniversity (suupervisor: Prrof. S.
ofYamamurra) Profession
nal Career
19966 Assistant professor, Tokyo
T
Instittute of Techhnology20077–present
Associatee professor, Tokyo Instiitute of Techhnology
 Research Interests
I1) Orrganic Syntthesis
2) Naatural Produuct Synthessis
3) Poolyphenol ChemistryCAwards19999 Chemiccal Frontier Award for YoungY
Chemmist, 1999
20001 Tejima Memorial Research
R
A
Award
(Nakaamura Prizee)
20002 Japan Chemical
C
Soociety Awarrd for Youngg Chemists
20005 Sankyoo Kagaku Aw
ward in Synnthetic Orgaanic Chemisstry
20008 Tokyo Tech
T
Awardd for Challenging Research20008 Merck––Banyu Lecctureship Aw
ward
20011 Tejima Memorial Research
R
A
Award
20013 Asian CoreC
Prograam Lecturesship Award
20016 SSOCJJ Daiichi-Saankyo Awarrd for Mediccinal Organnic Chemistrry
Recent Publications

1. "S
Synthesis andd Determinattion of the AbsoluteA
Configuration ofo Caviculariin by a Sym
mmetrization//
Assymmetrizatioon Approachh", H. Takiguuchi, K. Ohm
mori, K. Suzuuki, Angew. Chem. Int. Ed.
E 2013, 52,,
100472–10476.
2. "Annulation
A
Appproach to Doubly
D
Linkedd (A-type) Oligocatechinss: Synthesis oof (+)-Procyaanidin A2 andd(+)-Cinnamtannnin B1", Y. Itoo, K. Ohmorii, K. Suzuki, Angew. Chem
m. Int. Ed. 20014, 53, 10129
9–10133.
3. "F
Flavan–Isoflaavan Rearranngement: Biioinspired Sy
ynthetic Acccess to Isofllavonoids viia 1,2-Shift––Allkylation Seequence", K.
K Nakamurra, K. Ohm
mori, K. Suuzuki, Chem
m. Commun.. 2015, 51,,
70012–7014.
4. "TotalT
Synthesees of Perennipporides, M. Morita,MK. Oh
hmori, K. Suzzuki, Org. Lett. 2015, 17, 5634–5637
5
.
5. "T
Total Synthesiis of (+)-Viceenin-2", T.-C. Ho, K. Ohm
mori, K. Suzukki, Org. Lett. 2016, 18, 4488–4490.
6. "S
Stereocontrollled Total Synntheses of (––)-Rotenone anda (–)-Dalpaanol by 1,2-R
Rearrangemeent and SNArr
Oxxycyclizationns", K. Nakam
mura, K. Ohm
mori, K. Suzukki, Angew. Chem.
C
Int. Ed. 2017, 56, 18
82–187.

FRONTIER IN ORGANIC SYNTHESIS TOWARD MIDDLE MOLECULAR STRATEGY20

Aryl Fluorides, a Versatile Synthetic Platform
for Natural Product Synthesis
Ken Ohmori
Department of Chemistry, School of Science, Tokyo Institute of Technology
O-okayama, Meguroku, Tokyo 152-8551, Japan

Organofluorine compounds often show unusual chemical properties and behavior inorganic reactions. Among them, fluoroaromatic compounds（aryl fluorides) serve great
potential as versatile building blocks for synthesis of complex molecules. In this symposium,
the author will present some utilities of aryl fluorides in natural product synthesis, where
SNAr reaction and ortho-metalation/alkylation sequences are subjected as a key
transformation. Details will be discussed in this presentation.
Nu
Nu –
F

SN Ar
F
R–M

M

ortho-metalation--------------------------------------------------------------------------------------------------------------------

21

7th
h CCS/CSJ You
ung Chemistss ForumShu
uanhu Gaoo
Profeessor of Cheemistry
Shannghai Key LaboratoryLo Green Chhemistry andofd Chemicall Processes
Schoool of Chem
mistry and Molecular
M
Enngineering
East China Norm
mal Universsity
36633N Zhongshhan Road, Shanghai 2000062, P. R. China
Tel & Fax: (+866)-21-626044784
E-maail: shgao@@chem.ecnu.edu.cn
 Education
nal Backgroound20011 B.Sc., Lannzhou Univversity (supeervisor: Prof. Yongqianng Tu)
20066 Doctor off Philosophyy, Lanzhou University
U(supervisorr: Prof. Yonggqiang Tu)
 Profession
nal Career
20066-2010 Poost-doctoral fellow, UT Southwesteern Medicall Center at D
Dallas20100-now
Prrofessor at East
E China Normal
N
Uniiversity
 Research Interests
I1) Naatural produucts total syynthesis
2) MedicalM
chem
mistry Awards
20166
ACP-L
Lecture Awaards (to Honng Kong andd Japan)
20144
NSFC OutstandingO
g Young Sccholar Awarrd
20144
Young Investigatoor Award byy Chinese Chemical
C
Soociety20144
Thiemee Chemistryy Journal Aw
ward,
20133
New Ceentury Exceellent Talennts in University Awardd


Recent Publications

1. TotalT
Synthessis of Camptothecin andd Related Naatural Produccts by a Flexxible Strateg
gy, K. Li, J.
O Shuanhu Gao, Angew
Ou,
w. Chem. Int. Ed. 2016, 55
5, 14778–14783.
2. TotalT
Synthessis of Hamiggerans, X. Li,
L D. Xue, C.
C Wang, Shhuanhu Gao,, Angew. Ch
hem. Int. Ed.
2
2016,55, 99442–9946.
3. TotalT
Synthessis of Gracilaamine, Yingbbo Shi, Baocchao Yang, Shujun Cai, aand Shuanhu Gao Angew.
C
Chem.
Int. Edd. 2014, 53, 9539-9543.
9
4. AsymmetricA
Synthesis annd Biosyntheetic Implicatiions of (+)-F
Fusarisetin A
A, Jun Yin, ChengC
Wang,,
L Kong, Shhujun Cai, Shhuanhu Gao Angew.
Lili
A
Chem
m. Int. Ed. 20012, 51, 7786-7789.
5. TotalT
Synthessis of Cyanthhiwigins A, C,C G and H, Wang Chengg, Wang Dann and Gao Sh
huanhu Org.
L
Lett.
2013, 155, 4402-44055.

FRONTIER IN ORGANIC SYNTHESIS TOWARD MIDDLE MOLECULAR STRATEGY

Total Synthesis of Bioactive Natural Products: Efficiency and Diversity
Shuanhu Gao
Shanghai Key Laboratory of Green Chemistry and Chemical Processes,
School of Chemistry and Molecular Engineering, East China Normal University,
3663 Zhongshan N Rd, HuaShiDa, Putuo Qu, Shanghai, P. R. China 200062
The chemical synthesis of structurally interesting and biologically relevant natural
products has served as a driving force for developing new methodologies, testing the scope ofexisting synthetic methods. It also provides the platform for the further identification of their
specific biological targets and mechanistic mode of action. Our research interests are devoted
to develop synthetic useful methodologies to address natural target molecules that have novel
molecular structure, potent biological activity, and the potential for mechanistic studies.
In this presentation, I will introduce our recent progress in the total synthesis of
hamigerans, and structurally related natural products. A newly developed photo-induced
enolization/Diels–Alder strategy and its synthetic applications in the synthesis ofcordiachrome and anthrabenzoxocinone type natural products will also be discussed.

Figure 1. Target Molecules

22

23

7th
h CCS/CSJ You
ung Chemistss Forum

Hirooki Ogurii
Profeessor of Cheemistry
Depaartment of AppliedA
Cheemistry, Graaduate Schoool of Enginneering,
Tokyyo Universitty of Agricuulture and Technology
T
Addrress: 2-24-116 Nakacho, Koganei, Tokyo
T
184-8588, JAPAAN
Tel & Fax: (+81)-42-388-7037
E-maail: h_oguri@cc.tuat.acc.jp
 Education
nal Backgroound
19933 B.Sc., Tohhoku Univeersity (superrvisor: Prof.. Masahiro Hirama)H
19955 M.Sc., Grraduate School of Sciennce, Tohoku
u Universityy(supervisoor: Prof. Maasahiro Hiraama)
19988 Doctor off Science, Department
Do Chemistrry, Graduatee School off Science, Toofohoku
Universityy (supervisoor: Prof. Maasahiro Hiraama) Profession
nal Career
19966 JSPS Reseearch Fellow
wship for YoungY
Scien
ntist (DC2)19988 Assistant professor, Tohoku
T
Uniiversity (Grooup Head: Prof.
P
Masahhiro Hiramaa)
20033 Visiting Scientist,
S
Haarvard Univversity (Grouup Head: Prrof. Stuart L Schreiber))
20044 Associatee professor, Hokkaido University
U(Group(Headd: Prof. Hiddeaki Oikaw
wa)20133 JST-PRES
STO Researrcher (Moleecular Technnology, Research Superrvisor: Proff. Takashi
Kato)20155 Professor,, Tokyo Uniiversity of AgricultureA
and Technoology
 Research Interests
I1) Deesign and cooncise synthhesis of skeeletally diveerse natural products annd their analogs
2) Chhemical bioology with smallsor midd-sized syntthetic moleccules
3) Chhemo-enzym
matic synthhesis of natuural product analogs
 Awards
20011 The Inouee Research AwardA
for YoungY
Scien
ntists20022 The Younng Scientist’’s Research Award in Natural
N
Prodduct Chemisstry
20066 The Chem
mical Societty of Japan AwardA
for Young
Y
Chem
mists
20100 Banyu Chhemist Awarrd (2010)

Recent Publications

1.

““Biomimeticc assembly lines produucing naturall product annalogs: Straategies fromm a versatileemmanifoldto skeletallys
divverse scaffollds” Oguri, H.*
H Chem. Reec. 2016, 16,, 652.
“
“Synthesisof multiplyy substituteed 1,6-dihyddropyridiness through Cu(I)-catalyzed 6-endooccyclization”
Mizoguchi, H.; Watanaabe, R.; Minnami, S.; Oikkawa, H.; O
Oguri, H.* Org.
O
Biomol.
C
Chem.
2015,, 13, 5955.
""Biogenetica
ally inspired synthesis and skeletal diversificatiodon of indolee alkaloids " Mizoguchi,,
H Oikawa , H.; Oguri, H.*
H.;
H Nat. Cheem. 2014, 6, 57.
""Sequential[6+2], [2+22], [3+2] Annulations forf Rapid AssemblyA
off Multiple Fragments
F"
M
Mahendar,
V Oikawa, H.;V.;
H Oguri, H.* Chem. Co
ommun. 20133, 49, 2299.
""Generationof anti-trypaanosomal aggents throughh concise synnthesis and structural diversificationn
o sesquiterppene analogss " Oguri, H.*;of
H Hiruma, T.; Yamaggishi, Y.; Oikkawa, H.; Isshiyama, A.;;O
Otoguro,K.;; Yamada, H.;
H Ōmura, S.
S J. Am. Chem. Soc. 2011, 133, 70996. selected as the fronttccover.

2.

3.
4.
5.

FRONTIER IN ORGANIC SYNTHESIS TOWARD MIDDLE MOLECULAR STRATEGY

Development of Chemical Assembly Lines
Generating Skeletally Diverse Natural Products and Their Variants
Hiroki Oguria,bDepartment of Applied Chemistry, Graduate School of Engineering, Tokyo University ofAgriculture and Technology, 2-24-16 Nakacho, Koganei, Tokyo 184-8588, Japanb
JST-PRESTO, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012, Japana

Our research group aims to develop chemical assembly lines that concisely generate
natural products and their variants having different skeletal, stereochemical and functionalgroup properties. In this forum, I will introduce two topics: (1) Biogenetically-inspired
synthesis and skeletal diversification of indole alkaloids, (2) Design and de novo synthesis ofanti-malarial 6-aza-artemisinins. These approaches could pave the way to rapid andcost-effective production of skeletally diverse, readily modifiable, and natural
product-relevant molecules that have been inaccessible by other means.

References
1) Oguri, H.* Chem. Rec. 2016, 16, 652.
2) Mizoguchi, H.; Oikawa , H.; Oguri, H.* Nat. Chem. 2014, 6, 57.
3) Mizoguchi, H.; Watanabe, R.; Minami, S.; Oikawa, H.; Oguri, H.* Org. Biomol. Chem. 2015, 13,5955. 4) Reddy, B. K.; Hiruma, T.; Mizoguchi, H.; Ochiai, K.; Suzuki, S.; Oikawa, H.; Ishiyama,A.; Hokari, R.; Iwatsuki, M.; Otoguro, K.; Ōmura, S.; Oguri, H. submitted.

24

25

7th
h CCS/CSJ You
ung Chemistss Forum

Xiaooguang Lei
L
Profeessor of Cheemistry
Depaartment of ChemicalC
Biology, Colllege of Cheemistry, Pekking Universsity
Addrress: 202 Chhengfu Roaad, Beijing 100871,
1
ChiinaTel & Fax: (+866)-10-627600292
E-maail: xglei@ppku.edu.cn
 Education
nal Backgroound20011 B.Sc., Pekking Univerrsity (supervvisor: Prof. Jianbo Wanng)
20066 Ph.D., Deepartment off Chemistryy, Boston Un
niversity (suupervisor: P
Prof. John Porco)P Profession
nal Career
20066-2008 Poostdoc Fellow
w, Columbiia Universitty (supervisor: Prof. Saamuel Danisshefsky)
20099-2014 Priincipal Inveestigator, Naational Instiitute of Biollogical Scieences (NIBS
S), Beijing
20144- now Proofessor, Pekking Univerrsity
 Research Interests
I
Natuural product total syntheesis, Chemiical biology
y, and Mediccinal chemistryAwards2017 Tetrahedronn Young Inveestigator Awaard in Bioorg
ganic and Meedicinal Chem
mistry2017 Swiss Chem
mical Societyy Distinguishhed Lecturesh
hip Award
2017 The David Ginsburg
G
Meemorial Lectuureship Award
2016 Asian Core Program Lecctureship Aw
ward2015 Chemical Society of Jappan Distinguiished Lecturreship Awardd
2014 Roche Younng Investigattor Award
2013 Young Chem
mical Biologgist Award byy the Internattional Chemiical Biology SocietyRecent Publications

1. Liiu, X.; Dongg, T.; Zhou, Y.;
Y Huang, N.;
N Lei, X.* “Exploring the Bindingg Proteins off Glycolipidss
wiith Bifunctioonal Chemicaal Probes” An
ngew. Chem
m. Int. Ed. 20016, 55, 143330-14334.
2. Liiu, W.; Li, H.; Cai, P.; Wang, Z.; Yu, Z-X.; Lei, X.*
X “Scalabble Total SynthesisS
off
Juungermannennones B and C”
C Angew. Chem.
C
Int. Ed.
E 2016, 55, 3112-3116.
3. Hoong, B.; Li, C.; Wang, Z.; Chen, J.;
J Li, H.*; Lei, X.* “Enantioselecctive Total SynthesisS
off(-))-Incarviatonne A” J. Am. Chem. Soc. 2015, 137, 11946-119499.
4. Lii, C.; Dong, T.; Li, Q.; Lei, X.* “P
Probing the Anti-cancerr Mechanism
m of (-)-Ainnsliatrimer A
thrrough Diverrted Total Syynthesis and Bioorthogon
nal Ligation” Angew. Ch
Chem. Int. Ed.
E 2014, 53,,
122111-12115.
5. Lii, Q.; Dong, T.; Liu, X.; Lei, X.* “A
A Bioorthogo
onal Ligationn Enabled byy Click Cyclloaddition off
o-Quinolinonee Quinone MethideM
and VinylV
Thioethher” J. Am. Chem.
C
Soc. 22013, 135, 49996-4999.
6. Wang,W
G.*; Wang,W
X.; Yuu, H.; Wei, S.;
S Williams, N.; Holmees, D. L.; Haalfmann, R.;; Naidoo, J.;;W
Wang,
L.; Li, L.; Chen, S.;
S Harran, P.;
P Lei, X.*; Wang, X.* “Small Molecule Activ
vation of theeTR
RAIL Recepttor DR5 in Human
H
Canceer Cells” Naature Chem. Biol.
B
2013, 99, 84-89.
7. Suun, L.; Wang, H.; Wang, Z.;
Z He, S.; Chen,
C
S.; Liaoo, D.; Wang, L.; Yan, J.; L
Liu, W.; Lei, X.*; Wang,,
X..* “Mixed Lineage
L
Kinnase Domainn-like Protein
n Mediates Necrosis Signaling Dow
wnstream off
RIIP3 Kinase” Cell 2012, 148, 213-227.
8. Lii, C.; Dian, L.; Zhang, W.; Lei, X.*
X “Biomim
metic Syntheeses of (-)-G
Gochnatiolides A-C andd(-))-Ainsliadim
mer B” J. Am.. Chem. Soc.. 2012, 134, 12414-12417.

FRO
ONTIER IN ORGANIC SYNTHESIS TOWA
ARD MIDDLEE MOLECULAR
R STRATEGY

Coomplex Natural
N
Prroduct as a Driving
g Force foor Discoveery in Org
ganic
S
Synthesis
and Chem
mical Biollogy
Xiaoguang Lei
Departm
ment of Cheemical Bioloogy, Collegee of Chemisstry, Peking University,
Beijingg 100871, P.
P R. China

Complex nattural produccts providee tremendou
us opportunnities to shaape the lan
ndscape oforganiic synthesiss, as well as to impaact the biom
medical ressearch and drug disco
overy. My
laboraatory conduucts researrch at thee interfacee between chemistryy and biollogy. We
systemmatically usse bioactivee small moolecules, paarticularly naturalnprodducts, to sttudy their
biologgical functioons, elucidaate molecular mechaniisms of the important biological pathways,p
and deevelop noveel therapeutiic agents foor currently intractable diseases. H
Herein, I wou
uld like todisclosse our receent endeavoors towardss the efficieent synthesses of a nuumber of sttructurally
compllex and bioaactive naturral productss as well ass using the natural prooduct-basedd chemicalprobess to dissect programmep
ed cell deathh.

26

7th CCS-CSJ Young Chemists Forum 2017
－Frontier in Organic Synthesis toward Middle Molecular Strategy－■Date

March 18th (Sat), 2017 9:00-17:10■VenueS2; Room J24, House B, Bldg. 4,
Hiyoshi Campus, Keio University
Yokohama, Kanagawa, Japan■Hosted by
The Chemical Society of Japan (CSJ)
Co-hosted by The Chinese Chemical Society (CCS)

Publication: March 2017
Publisher: The Chemical Society of Japan
1-5, Kanda-Surugadai, Chiyoda-ku Tokyo, 101-8307, Japan
Copyright: The Chemical Society of Japan

。

o 忠o
/ y \
’

ーl

riM句

o I
OA Ol
l
rlk o l① Suzuki-Coupling of Ar-Cl substrates② Borylation of bulky Ar-Cl substrates③ Regioselective C-H borylation④ Caged phoshines allow catalysts to be stable in the air.
⑤ Palladium is separated from the products by Celite刊tration. 1>

C臼

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um盟国

mm盟国
附（OA�）� 0�5 mol%R0--CI
pinB-Bpin 1.0eq.
KOAc3.0eq.
toluene, 16 h

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cfCI

Silica-SMAP 0.5 mol%Pd(0Ac)2 0.5 or 1.0 mol%

Entry

8 0℃，8 5% 90℃，89% 90℃，90% 1110℃，72%

110℃，83%

Borylation of bulky Ar-Cl substrates

2
3
4
5

pinB-Bpin 1.0eq.
KOAc3.0eq.
benzene, 16 h
LigandSilica-SMAP
SPhos
SPhos
XPhos
XPhos

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[Pd］／山
1:1
1:1
1:2
1:1
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。

Depending Silica-SMAP is a highly on the substrate,
active than Buchwald Ligand .

�亙亙1) Hamasaka, G., Ochida, K , Hara, K., and Sawamura, M.: Angew. Chem. Int. Ed., 46, 5381 (2007).
2) Kawamorita, S., Ohmiya, H., lwai, T. and Sawamura, M. :Angew. Chem. Int. Ed., 50, 8363 (2011).
3) Kawamorita, S., Ohmiya, H.,Hara, K., Fukuoka, A. and Sawamura, M.: J. Am. Chem. Soc., 14, 5058 (2009).

mzml園
193-17453

Silica-SMAP

Wako Pure Chemical Industries, Ltd.

Organic Synthesis

On line Catalog: www.e-reagent.com
labchem@wakousa.com
USA:
Eu rope:biochem@wako-chemicals.decservice@wako-chem.co.jp
Others:「