The Nakanishi Symposium
on Natural Products & Bioorganic Chemistry

Nagoya University
March 27, 2014

Sponsored by
The Chemical Society of Japan&The American Chemical Society

― Table of Contents ―Profile of Professor Jerrold Meinwald;
the Prize Winner of the Nakanishi Prize 2014……

2

Program of the Award Ceremonyof the Nakanishi Prize & Nakanishi Symposium……

5“Chemistry and Biology of Nyctinastic Plant
Movement”
Prof. Minoru Ueda (Tohoku University)……

6“Toward an Ideal Synthesis of Bioactive
Molecules through Direct Arene Assembling”
Prof. Junichiro Yamaguchi (Nagoya University)……

7“Exploration of New Juvenile Hormone ofHeteropteran Insects”
Prof. Tetsuro Shinada (Osaka City University)……

9“Chemical Ecology of Insect－Plant Interactions― Ecological Roles of Phytochemicals”
Prof. Ritsuo Nishida (Kyoto University)…… 12

Award Lecture“Exploring the Chemistry of Biotic Interactions”
Prof. Jerrold Meinwald (Cornell University)…… 13－1－

Jerrold Meinwald
Professor Emeritus, Cornell University■Department Appointments
Chemistry and Chemical Biology (CHEM)■Graduate Fields
Chemistry and Chemical Biology■Other Affiliations
American Academy of Arts & Sciences, Secretary■Keywords
Biosynthesis of biologically active natural products, chemicalecology－2－■ResearchIsolation and identification of biologically active compounds
from insect and other arthropod sources
Pheromone and chemical defensive systems of arthropods
Identification of the messenger molecules involved and theunderstanding of the underlying signal transduction pathways■Selected Publications
1. Eisner, T.; Meinwald, J. Alkaloid-Derived Pheromones andSexual Selection in Lepidoptera. Pheromone Biochemistry andMolecular Biology, G. J. Blomquist and R. C. Vogt, Eds., Elsevier
Academic Press, London, 2003, pp. 341–368.
2. Taggi, A.E.; Meinwald, J.; Schroeder, F. A New Approach to
Natural Products Discovery Exemplified by the Identification of
Sulfated Nucleosides in Spider Venom. J. Am. Chem. Soc, 2004,126 (33), 10364.
3. Schroeder, F.C.; Weibel, D.B.; Meinwald, J. Chiral Silylation
Reagents: Determining Configuration via NMR-Spectroscopic
Coanalysis. Organic Letters, 2004, 6, 3019.
4. Meinwald, J. Personal Reflections on Receiving the Roger
Adams Award in Organic Chemistry. JOC , 2005, 70, 4903.
5. Gronquist, M.; Meinwald, J.; Eisner, T.; Schroeder, F.
Exploring Uncharted Terrain in Nature's Structure Space Using
Capillary NMR Spectroscopy: 13 Steroids from 50 Fireflies. JACS
2005, 127 (31), 10810.
■Awards and Distinctions
 American Chemical Society Ernest Guenther Award; Arthur C. Cope Scholar
 Tyler Prize for Environmental Achievement (with ThomasEisner)－3－ International Society of Chemical Ecology Silver Medal Gustavus John Esselen Award for Chemistry in the PublicInterest(with Thomas Eisner)
 Czech Academy of Sciences Heyrovsky Medal 2005 American Chemical Society Roger Adams Award inOrganic Chemistry 2006 Grand Prix, la Maison de la Chimie (with ThomasEisner) 2013 Benjamin Franklin Medal in Chemistry－4－Nakanishi Symposium 2014
Organized by：Nakanishi Symposium Organizing Committee
Co-organized by: Chemical Society of Japan,
Division of Natural Products Chemistry & Biological Science

Date March 27th, 2014, 13:30–17:30
Venue Nagoya University (Higashiyama Campus)
Program■13:30–14:00 Award Ceremony of the Nakanishi Prize 2014
Chair
Prof. Kazuo Tachibana (The University of Tokyo)
Prize Winner of the Nakanishi Prize 2014:
Prof. Jerrold Meinwald (Cornell University)■14:00–17:30 Nakanishi Symposium
Chair
Prof. Michio Murata (Osaka University)◆14:00–“Chemistry and Biology of Nyctinastic Plant Movement”
Prof. Minoru Ueda (Tohoku University)◆14:35–“Toward an Ideal Synthesis of Bioactive Molecules throughDirect Arene Assembling”
Prof. Jun’ichiro Yamagushi (Nagoya University)
Chair
Prof. Minoru Ueda (Tohoku University)◆15:10–“Exploration of New Juvenile Hormone of Heteropteran Insects”
Prof. Tetsuro Shinada (Osaka City University)◆15:45–“Chemical Ecology of InsectPlant Interactions－ Ecological Roles of Phytochemicals”
Prof. Ritsuo Nishida (Kyoto University)
Chair
Prof. Kazuo Tachibana (The University of Tokyo)◆16:20– Award Lecture“Exploring the Chemistry of Biotic Interactions”
Prof. Jerrold Meinwald （Cornell University）－5－Chemistry and Biology of Plant Leaf-movement
Minoru Ueda
Department of Chemistry, Tohoku University
ueda@m.tohoku.ac.jp“The movements of plant” is historic research field in biology.
It is well known that Charles Darwin is a pioneer of this field. We
have been engaged in the bioorganic studies on this intriguing plant
behavior.
We identified 12-O--D-glucopyranosyljasmonic acid (JAG)1
as the bioactive metabolite inducing nyctinastic leaf-folding ofSamanea saman. 2, 3 JAG was completely inactive with respect toactivation of typical JA responses and triggers leaf-folding throughCOI1-dependent mechanism.3 The addition of JAG mediates thegeneration of second messenger in the extensor motor cell and induce
the activation of outward-rectifying potassium channel. Additionally,
JAG have identified as a trap-closing endogenous factor of Venus’sFlytrap.4 This movement is also known to be classified in an
ion-channel regulated behavior of plant. We found unique function of
JAG as an endogenous mediator of “plant movements”.
References:
1. Tetrahedron, 56, 8101–8105 (2000).
2. Angew. Chem. Int. Ed., 47, 7289–7292 (2008).
3. Plant Physiology, 155, 1226–1236 (2011).
4. ChemBioChem, 11, 2378–2383 (2010).

－6－

Toward an Ideal Synthesis of Bioactive Molecules
Through Direct Arene Assembling
Junichiro Yamaguchi
Department of Chemistry,
Graduate School of Science, Nagoya University
junichiro@chem.nagoya-u.ac.jp
Biaryls and heterobiaryls are ubiquitous motifs inpharmaceuticals, natural products, and organic materials alike, andtherefore, the construction of these scaffolds has been a topic of great
importance in chemistry. Recently, C–H coupling of aromaticcompounds using transition metal catalysts has garnered muchattention from the synthetic chemistry community as anext-generation coupling method for constructing (hetero)biaryl
motifs.1 Although the development of new reactions and catalysts
continues to evolve at a rapid pace, successful applications of thismethod to the synthesis of natural products and pharmaceuticals arestill rare.2 Thus, our research program has focused onsynthesis-oriented methodology development in catalytic C–H
coupling (direct arene–assembling reactions). As a result, more thanten new C–H coupling reactions of heteroarenes such as 1,3-azoles,indoles, pyrroles, azines, and thiophenes have been developed andutilized for the rapid synthesis of bioactive molecules such as natural
products and pharmaceutical candidates. Furthermore, the method oflate-stage C–H coupling can be highly relevant for medicinal
chemistry. In this symposium, I would like to talk our recent progressof toward an ideal synthesis of bioactive molecules through direct
arene assembling.
－7－References:
1. Yamaguchi, J.; Itami, K. “Biaryl Synthesis through Metal-Catalyzed
C–H Arylation”, Metal-Catalyzed Cross-Coupling and More,Wiley–VCH, 2014, 1315
2. Yamaguchi, J.; Yamaguchi, A. D; Itami, K. Angew. Chem. Int.
Ed. 2012, 51, 8960.

－8－Exploration of New Juvenile Hormone ofHeteropteran Insects
Tetsuro Shinada
Graduate School of Science, Osaka City University
shinada@sci.osaka-cu.ac.jp

The insect juvenile hormone (JH) is an acyclic terpenoid that
regulates many aspects of insect physiology, such as metamorphosis,
reproduction, diapause, and polyphenisms (Fig. 1).1 The presence ofJH was first discovered by Wigglesworth in 1934 in theblood-sucking bug, Rhodnius prolixus (suborder Heteroptera, orderHemiptera) as a humoral factor that prevents metamorphosis of thefinal instar nymph into an adult.2 The structure of JH I (1) in thececropia moth was first elucidated in 1967.3 Since then, several JHs
2-6 have been reported.1－9－Heteropteran insects are a major insect group including ca. 40,000species. In this group, several serious pests of crops and gardens, andvectors of the Chagas parasite are included. Although thephysiological study of heteropterans is one of the important subjects
in this research area, the structure of heteropteran JH has remainedunsolved. We tackled this challenge and solved the structure of a newJH, JHSB,3 in a stink bug, Plautia stali by a new chemical library
approach (Fig. 2).4 In this presentation, the details of new chemical
library approach and its application to the exploration of JHSB3 inother heteropteran insects will be described.
－10－References:
1. Morgan, E. D.; Wilson, I. D.; Mori, K. “Comprehensive Natural
Products Chemistry”;Barton, D. H. R., Nakanishi, K., Eds.
Miscellaneous Natural Products Including Marine Natural Products,Pheromones, Plant Hormones, and Aspects of Ecology; Pergamon:
Oxford, 1999; Vol. 8, pp 263–369.
2. Wigglesworth, V. B. Q. J. Microsc. Sci. 1934, 77, 191–222.
3. Röller, H.; Dahm, K. H.; Sweely, C. C.; Trost, B. M. Angew. Chem. Int.
Ed. Engl. 1967, 6, 179–180.
4. (a) Kotaki, T.; Shinada, T.; Kaihara, K.; Ohfune, Y.; Numata, H. Org.
Lett. 2009, 11, 5234-5237. (b) Kotaki, T.; Shinada, T.; Kaihara, K.;
Ohfune, Y.; Numata, H. J. Insect Physiol. 2011, 57, 147–152.

－11－Chemical Ecology of InsectPlant Interactions– Ecological Roles of Phytochemicals
Ritsuo Nishida
Graduate School of Agriculture, Kyoto University
ritz@kais.kyoto-u.ac.jp
Plants produce a diverse array of secondary metabolites as
chemical barriers against herbivores. Phytophagous insects are highlyadapted to these allelochemicals and may use such unique substances
as specific host-finding cues, defensive substances of their own (allomones), and even as sex pheromones or their precursors byselectively sensing, incorporating and/or processing thesephytochemicals.
Caterpillars of a giant danaine butterfly, Idea leuconoe,
selectively feed on Parsonsia laevigata (Apocynaceae), by sensing
specific metabolites in the host plant, and sequester a series of
poisonous pyrrolizidine alkaloids to protect themselves frompredators. The males biotransform alkaloids to danaidone and aunique -1actone, and emit a bouquet of volatiles from “hairpencils”
to arrest a female (see below). The female can verify a male’s
defensive quality via the pheromonal ingredients. This exemplifies an
ecological adaptation mechanism via plant secondary metabolites in
the highly diverse interactions between insects and plants.

References:
R. Nishida, Biosci. Biotech. Biochem. 78 (1) (2014).
－12－

Exploring the Chemistry of Biotic Interactions
Jerrold Meinwald
Professor Emeritus, Cornell University
circe@cornell.edu

The study of the chemistry of “natural products” has
led to the rich development of much of what we know aboutorganic chemistry. However, it was not until the mid-20thcentury that the significance of natural products from theviewpoint of the producing organisms became a subject ofinterest to chemists. Some examples of our studies ofarthropod defensive chemistry will be presented, and therelationship between plant defensive chemistry and insect
chemical signaling will be discussed. Based on this andother examples, a plausible mechanism for the evolution ofpheromones will be presented. The study of chemical
ecology is still in its infancy, and it will be important topreserve the earth’s biodiversity so as to learn aboutchemical interactions of potential importance to medicine,
agriculture, and everyday life.

－13－Minoru Ueda: born in Nagoya, 1965 andgraduated from Konan University (B 1989),earned his PhD (1994, Nagoya Unversity,Prof. Minoru Isobe), and became AssistantProfessor, Department of Chemistry, KeioUniversity(1994–1999),
Lecturer,
Department of Chemistry, Keio University(1999–2001),
Associate
Professor,
Department of Chemistry, Keio University(2001–2004), and Professor, Department ofChemistry, Tohoku University (2004–). He received awards including
Japan Chemical Society Awards for Young Chemists (2000), TheTokyo Techno Forum Gold Medal (2003), and The Japanese Society
for Chemical Regulation of Plants Awards (2013).

Junichiro Yamaguchi: born in 1979 andgraduated from Tokyo University ofScience (B. 2002), PhD, Tokyo Universityof Science (Prof. Yujiro Hayashi) 2007,
Postdoctoral fellow, The Scripps ResearchInstitute (2007–2008, Prof. Baran),
Assistant Professor, Faculty of Science,
Nagoya University (2008–2012), Associate
Professor, Faculty of Science, NagoyaUniversity (2012–). Young Scientist’s
Research Award in Natural Product Chemistry, Japan (2011),
The Chemical Society of Japan Award for Young Chemists (2013),
Banyu Chemist Award (2013), and Thieme Chemistry Journal Award(2014).

－14－Tetsuro Shinada: born in Hyogo, 1965 andgraduate from Setsunan University (B.
1987), Kobe Pharmaceutical University(PhD, 1992, Prof. Ichiya Ninomiya).
Postdoctoral fellow: Texas A & M
University (1992–1994, Prof. D. H. R.
Barton), Suntory Institute for Bioorganic
Research (1994–1996, Prof. T. Nakajima).
Academic position: Lecturer, Department ofMaterial Science, Osaka City University(1996–2003, Prof. Y. Ohfune Lab.), Associate Professor, Graduate
School of Material Science, Osaka City University (2004–2010),
Professor, Graduate School of Material Science, Osaka City
University (2010– ). Award of Kansai Branch, The Society ofSynthetic Organic Chemistry, Japan (2008).

Ritsuo Nishida: born in Mie, 1949 andgraduated from Mie University (1972). PhD,Kyoto University (Prof. Hiroshi Fukami)
1977. Research Associate, NY State
Agricultural Experiment Station, Cornell
University (1977–1979, Prof. W. S. Bowers;
1979–1980, Prof. W. L. Roelofs). AssistantProfessor of Faculty of Agriculture, Kyoto
University(1980–1992),
Associate
Professor (1992–2003), Professor ofGraduate School of Agriculture, Kyoto University (2003–). Awards:
Research Award by Japanese Society of Applied Entomology andZoology, 1996. The Japan Bioscience, Biotechnology andAgrochemistry Society Senior Scientist Award, 2013.

－15－The Recipients of the Prize hereto are:19961997
1998
1999
2000
2001
2002
2003
2004
2005

Yoshimasa Hirata*
2006
Frank H. Westheimer 2007
Albert J. Eschenmoser* 2008
Jeremy R. Knowles
2009
Satoshi Omura*
2010
John D. Roberts
2011
Sir Jack Baldwin*
2012
A. Ian Scott2013
Isao Kitagawa*
2014
Stephen J. Benkovic

Takeshi Yasumoto*Hung-wen Liu
Michel Rohmer*
JoAnne Stubbe
Shosuke Yamamura*
C. Dale Poulter
Daisuke Uemura*
Arthur G. Palmer, III
Jerrold Meinwald**Selection and presentation made by the Chemical Society of Japan.

Organizing Committee:
ChairmanMinoru Ueda; (Tohoku University),
Members
Kazuo Tachibana (The University of Tokyo)
Michio Murata(Osaka University)
Motomasa Kobayashi (Osaka University)
Yasufumi Ohfune (Osaka City University)
Hiroyuki Osada(Riken)
Keisuke Suzuki(Tokyo Institute of Technology)
Daisuke Uemura (Kanagawa University)－16－

－17－