bluuebunny/crossref_metadata_2025 huggingface dataset:
Hexamethyl Dewar Benzene
Authors: Shama Sami A. , Wamser Carl C.
Published: November 2003

Hexamethyl dewar benzene

reactant: 100 g (1.85 mol) of 2‐butyne

product: hexamethyl Dewar benzene
Perhydro‐9b‐Boraphenalene and Perhydro‐9b‐Phenalenol
Authors: Negishi Ei‐ichi , Brown Herbert C.
Published: November 2003

Perhydro‐9b‐boraphenalene and perhydro‐9b‐phenalenol

intermediate:
cis,cis,trans
‐2‐(perhydro‐9′b‐phenalyl)‐1,3,2‐dioxaborole

product:
cis,cis,trans
‐perhydro‐9b‐phenalenol

product:
cis,trans
‐ and
cis,cis
‐perhydro‐9b‐boraphenalene
Photoprotonation of Cycloalkenes: Limonene to
p
‐Menth‐8‐en‐1‐yl Methyl Ether
Authors: Tise F. P. , Kropp P. J.
Published: November 2003

Photoprotonation of cycloalkenes: limonene to
p
‐menth‐8‐en‐1‐yl methyl ether

product:
cis
‐ and
trans
‐
p
‐menth‐8‐en‐1‐yl methyl ether

product: cyclohexyl methyl ether in 70% yield
Silylation of Ketones With Ethyl Trimethylsilacetate: (Z)‐3‐Trimethylsiloxy‐2‐Pentene
Authors: Kuwajima Isao , Nakamura Eiichi , Hashimoto Koichi
Published: November 2003

Silylation of ketones with ethyl trimethylsilacetate: (Z)‐3‐trimethylsiloxy‐2‐pentene

intermediate: ethyl trimethylsilylacetate

product: 3‐trimethylsiloxy‐2‐pentene
Generation and Reactions of Alkenyllithium Reagents: 2‐Butylbornene
Authors: Chamberlin A. Richard , Liotta Ellen L. , Bond F. Thomas
Published: November 2003

Generation and Reactions of Alkenyllithium Reagents: 2‐Butylbornene

reactant: 30.4 g (0.20 mol) of d‐camphor

product: 2‐Butylbornene

intermediate: 40.0 g (0.092 mol) of d‐camphor 2,4,6‐triisopropylbenzenesulfonylhydrazone

byproduct: bornylene
A General Synthetic Method for the Preparation of Methyl Ketones from Terminal Olefins: 2‐Decanone
Authors: Tsuji Jiro , Nagashima Hideo , Nemoto Hisao
Published: November 2003

A General synthetic method for the preparation of methyl ketones from terminal olefins: 2‐decanone

product: 2‐decanone
cis‐N
‐Tosyl‐3‐Methyl‐2‐Azabicyclo[3.3.0]Oct‐3‐Ene
Authors: Hegedus Louis S. , Holden Michael S. , McKearin James M.
Published: November 2003

cis
‐
N
‐tosyl‐3‐methyl‐2‐azabicyclo[3.3.0]oct‐3‐ene

reactant: 20.0 g (158 mmol) of
trans
‐2‐(2‐propenyl)cyclopentanol

reactant: 8.00 g (64 mmol) of
cis
‐2‐(2‐propenyl)cyclopentylamine

product:
cis‐N‐Tosyl‐3‐methyl‐2‐azabicyclo[3.3.0]oct‐3‐ene
.

reactant: 5.159 g (18.49 mmol) of
cis
‐1‐
N
‐tosyl‐2‐(2‐propenyl)cyclopentylamine

catalyst: Palladium(II) chloride–acetonitrile complex
Silylation of 2‐Methyl‐2‐Propen‐1‐ol Dianion: 2‐(Hydroxymethyl)Allyltrimethylsilane
Authors: Trost Barry M. , Chan Dominic M. T. , Nanninga Thomas N.
Published: November 2003

Silylation of 2‐methyl‐2‐propen‐1‐ol dianion: 2‐(hydroxymethyl)allyltrimethylsilane

intermediate: 4.25 g, bp 29–57°C (4 mm), and 45.8 g (52%) of 2‐(trimethylsiloxy)allyltrimethylsilane

product: 0.4 g, bp 22–54°C (4 mm), and 10.95 g (78%) of 2‐(hydroxymethyl)allyltrimethylsilane

byproduct: mineral oil

byproduct: 4–6% of a vinylsilane
Conjugate Allylation of α,β‐Unsaturated Ketones with Allylsilanes: 4‐Phenyl‐6‐Hepten‐2‐one
Authors: Sakurai Hideki , Hosomi Akira , Hayashi Josabro
Published: November 2003

Conjugate allylation of α,β‐unsaturated ketones with allylsilanes: 4‐phenyl‐6‐hepten‐2‐one

product: 4‐phenyl‐6‐hepten‐2‐one

product: 1‐methyl‐1‐trimethylsilylmethyl‐3‐n‐propylspiro[3,4]octan‐5‐one

product: 2,8a‐diallyl‐3,4,4a,5,6,7,8,8a‐octahydronaphthalene

product: CH
2
CH(CH
2
)
3
COCH
3

product: CH
2
C(CH
3
)
2
CH
2
CH
2
COCH
3

product: CH
2
CHCH
2
C(CH
3
)
2
CH
2
COCH
3

product: CH
2
C(CH
3
)CH
2
CH(Ph)CH
2
COCH
3

product: CH
2
CHCH(CH
3
)CH(Ph)CH
2
COCH
3

product: CH
2
CHCH
2
CH(Ph)CH
2
COCH
3
β‐Haloacetals and Ketals: 2‐(2‐Bromoethyl)‐1,3‐dioxane and 2,5,5‐Trimethyl‐2‐(2‐bromoethyl)‐1,3‐dioxane
Authors: Stowell J. C. , Keith D. R. , King B. T.
Published: November 2003

β‐Haloacetals and ketals: 2‐(2‐bromoethyl)‐1,3‐dioxane and 2,5,5‐trimethyl‐2‐(2‐bromoethyl)‐1,3‐dioxane

product: 2‐(2‐Bromoethyl)‐1,3‐dioxane

product: 2,5,5‐Trimethyl‐2‐(2‐bromoethyl)‐1,3‐dioxane

unknown: 1,9‐diphenylnona‐1,3,6,8‐tetraen‐5‐one

intermediate: 3‐bromopropanal

intermediate: 4‐bromo‐2‐butanone
Cycloundecanecarboxylic Acid
Authors: Hamada Yasumasa , Shioiri Takayuki
Published: November 2003

Cycloundecanecarboxylic acid

intermediate: 1‐(
N
‐pyrrolidino)‐1‐cyclododecene

product: cycloundecanecarboxylic acid

intermediate: diphenyl (cycloundecyl‐1‐pyrrolidinylmethylene)phosphoramidate
α‐Allenic Esters from α‐Phosphoranylidene Esters and Acid Chlorides: Ethyl 2,3‐Pentadienoate
Authors: Lang Robert W. , Hansen Hans‐Jürgen
Published: November 2003

α‐Allenic esters from α‐phosphoranylidene esters and acid chlorides: Ethyl 2,3‐pentadienoate

reactant: 34.8 g (0.10 mol) of ethyl (triphenylphosphoranylidene)acetate

product: ethyl 2,3‐pentadienoate
Preparation of Chiral, Nonracemic γ‐Lactones by Enzymecatalyzed Oxidation of
meso
‐Diols: ( + )‐(1
R
,6
S
)‐8‐Oxabicyclo[4.3.0]Nonan‐7‐One
Authors: Jones J. Bryan , Jakovac Ignac J.
Published: November 2003

Preparation of chiral, nonracemic γ‐lactones by enzymecatalyzed oxidation of
meso
‐diols: ( + )‐(1
R
,6
S
)‐8‐oxabicyclo[4.3.0]nonan‐7‐one

product: ( + )‐(1
R
,6
S
)‐8‐oxabicyclo[4.3.0]nonan‐7‐one
Enantioselective Epoxidation of Allylic Alcohols: (2
S
,3
S
)‐3‐Propyloxiranemethanol
Authors: Hill J. Gordon , Sharpless K. Barry , Exon Christopher M. , Regenye Ronald
Published: November 2003

Enantioselective epoxidation of allylic alcohols: (2
S
,3
S
)‐3‐propyloxiranemethanol

product: (2
S
,3
S
)‐3‐propyloxiranemethanol
(2
SR
,3
RS
)‐2,4‐Dimethyl‐3‐hydroxypentanoic Acid
Authors: Bal B. , Buse C. T. , Smith K. , Heathcock Clayton H.
Published: November 2003

(2
SR
,3
RS
)‐2,4‐Dimethyl‐3‐hydroxypentanoic acid

solvent: 31 mL (0.22 mol) of diisopropylamine

solvent: 14.4 g (0.20 mol) of 2‐methylpropanal

intermediate: 12.0 g of 5‐hydroxy‐2,4,6‐trimethyl‐2‐(trimethylsiloxy)heptan‐3‐one (10.8 g, 41 mmol of ketone from a 90 : 10 mixture from Part A)

product: (2
SR
,3
RS
)‐2,4‐dimethyl‐3‐hydroxypentanoic acid

intermediate: α,γ,γ‐trimethylbutyrolactone
(
S
)‐(+)‐γ‐Butyrolactone‐γ‐carboxylic Acid
Authors: Gringore Olivier H. , Rouessac Francis P.
Published: November 2003

(
S
)‐(+)‐γ‐butyrolactone‐γ‐carboxylic acid

reactant: 294 g (2 mol) of L‐glutamic acid

product: (+)‐γ‐butyrolactone‐γ‐carboxylic acid
2,3‐
O
‐Isopropylidene‐
D
‐Erythronolactone
Authors: Cohen Noal , Banner Bruce L. , Laurenzano Anthony J. , Carozza Louis
Published: November 2003

2,3‐
O
‐isopropylidene‐
D
‐erythronolactone

intermediate:
D
‐erythronolactone

product: 2,3‐
O
‐isopropylidene‐
D
‐erythronolactone
tert‐Butoxycarbonylation of Amino Acids and their Derivatives:N‐tert‐Butoxycarbonyl‐l‐phenylalanine
Authors: Keller Oskar , Keller Walter E. , Look Gert van , Wersin Gernot
Published: November 2003

tert‐Butoxycarbonylation of amino acids and their derivatives:N‐tert‐butoxycarbonyl‐l‐phenylalanine

reactant: 223 g (1 mol) of di‐tert‐butyl dicarbonate

product: N‐tert‐butoxycarbonyl‐L‐phenylalanine

product: Boc‐Ala‐OH

product: Boc‐β‐Ala‐OH

product: Boc‐Arg‐OH

product: Boc‐Arg(NO2)‐OH

product: Boc‐Asn‐OH

product: Boc‐Asp(OBzl)‐OH

product: Boc‐Cys(Bzl)‐OH

product: (Boc‐Cys‐OH)2

product: Boc‐Gln‐OH

product: Boc‐Glu(OBzl)‐OH

product: Boc‐Gly‐OH

product: Boc‐His(Boc)‐OH

product: Boc‐Ile‐OH

product: Boc‐Leu‐OH

product: Boc‐Lys(Boc)‐OH

product: Boc‐Lys(CBZ)‐OH

product: Boc‐Met‐OH

product: Boc‐Met‐OH

product: Boc‐Pro‐OH

product: Boc‐Ser‐OH

product: Boc‐Ser(Bzl)‐OH

product: Boc‐Thr‐OH

product: Boc‐Trp‐OH

product: Boc‐Trp‐(FOR)‐OH

product: Boc‐Tyr‐OH

product: Boc‐Tyr‐OH

product: Boc‐Tyr(Bzl)‐OH

product: Boc‐Tyr(2,6‐Cl2‐Bzl)‐OH

product: Boc‐Val‐OH
N‐
tert
‐Butoxycarbonyl‐l‐phenylalanine
Authors: Paleveda William J. , Holly Frederick W. , Veber Daniel F.
Published: November 2003

N‐
tert
‐butoxycarbonyl‐l‐phenylalanine

product: tert‐butoxycarbonyl‐L‐phenylalanine
Esterification of Carboxylic Acids with Dicyclohexylcarbodiimide/4‐Dimethylaminopyridine:tert‐Butyl Ethyl Fumarate
Authors: Neises B. , Steglich Wolfgang
Published: November 2003

Esterification of carboxylic acids with dicyclohexylcarbodiimide/4‐dimethylaminopyridine:tert‐butyl ethyl fumarate

reactant: 45.59 g (0.22 mol) of dicyclohexylcarbodiimide

product: tert‐butyl ethyl fumarate
Anodic Oxidation of
N
‐Carbomethoxypyrrolidine: 2‐Methoxy‐
N
‐Carbomethoxypyrrolidine
Authors: Shono T. , Matsumura Y. , Tsubata K.
Published: November 2003

Anodic oxidation of
N
‐carbomethoxypyrrolidine: 2‐methoxy‐
N
‐carbomethoxypyrrolidine

intermediate: 119–121 g (92–94%) of
N
‐carbomethoxypyrrolidine, bp 64°C/1.3 mm

product:
2‐Methoxy‐N‐carbomethoxypyrrolidine
.

byproduct:
N
‐carbomethoxy‐2,5‐dimethoxypyrrolidine
Conversion of Methyl Ketones into Terminal Alkynes: (
E
)‐Buten‐3‐ynyl‐2,6,6‐trimethyl‐1‐cyclohexene
Authors: Negishi Ei‐ichi , King Anthony O. , Tour James M.
Published: November 2003

Conversion of methyl ketones into terminal alkynes: (
E
)‐buten‐3‐ynyl‐2,6,6‐trimethyl‐1‐cyclohexene

product: (E)‐buten‐3‐ynyl‐2,6,6‐trimethyl‐1‐cyclohexene
β‐Dimethylaminomethylenation:
N,N
‐Dimethyl‐
N
′‐
p
‐tolylformamidine
Authors: Gupton John T. , Andrews Steven A.
Published: November 2003

β‐Dimethylaminomethylenation:
N,N
‐dimethyl‐
N
′‐
p
‐ tolylformamidine

intermediate: [3‐(Dimethylamino)‐2‐azaprop‐2‐en‐1‐ylidene]dimethylammonium chloride

product:
N,N
‐dimethyl‐
N
′‐
p
‐tolylformamidine
1,3‐Dimethylimidazole‐2‐thione
Authors: Benac Brian L. , Burgess Edward M. , Arduengo Anthony J.
Published: November 2003

1,3‐Dimethylimidazole‐2‐thione

reactant: 44.8 g (0.20 mol) of 1,3‐dimethylimidazolium iodide

product: 1, 3‐dimethylimidazole‐2‐thione
(
S
)‐( + )‐2‐(
p
‐Toluenesulfinyl)‐2‐Cyclopentenone: Precursor for Enantioselective Synthesis of 3‐Substituted Cyclopentanones
Authors: Hulce Martin , Mallomo John P. , Frye Leah L. , Kogan Timothy P. , Posner Gary H.
Published: November 2003

(
S
)‐( + )‐2‐(
p
‐toluenesulfinyl)‐2‐cyclopentenone: Precursor for enantioselective synthesis of 3‐substituted cyclopentanones

intermediate: 57.5 g of crude methyl
p
‐toluenesulfinate

intermediate: (
S
)‐( + )‐2‐(
p
‐toluenesulfinyl)‐2‐cyclopentenone ethylene ketal

product: (
S
)‐( + )‐2‐(
p
‐toluenesulfinyl)‐2‐cyclopentenone
Tosylhydrazone Salt Pyrolyses: Phenyldiazomethanes
Authors: Creary Xavier
Published: November 2003

Tosylhydrazone salt pyrolyses: phenyldiazomethanes

intermediate: benzaldehyde tosylhydrazone

product: phenyldiazomethane

product: p‐MeC
6
H
4
CHN
2

product: m‐MeC
6
H
4
CHN
2

product: p‐FC
6
H
4
CHN
2

product: m‐FC
6
H
4
CHN
2
Acetone Trimethysilyl Enol Ether
Authors: Walshe Nigel D. A. , Goodwin Graham B. T. , Smith Graham C. , Woodward Frank E.
Published: November 2003

Acetone trimethysilyl enol ether

product: silyl enol ether of acetone
3,3‐Dimethyl‐1,5‐Diphenylpentane‐1,5‐dione
Authors: Narasaka Koichi
Published: November 2003

3,3‐Dimethyl‐1,5‐diphenylpentane‐1,5‐dione

intermediate: isopropylideneacetophenone

catalyst: Titanium tetrachloride (7.7 mL)

product: 3,3‐dimethyl‐1,5‐diphenylpentane‐1,5‐dione
Methylenation of Carbonyl Compounds: (+)‐3‐Methylene‐
cis
‐
p
‐methane
Authors: Lombardo Luciano
Published: November 2003

Methylenation of carbonyl compounds: (+)‐3‐Methylene‐
cis
‐
p
‐methane

intermediate: (+)‐isomenthone

product: (+)‐3‐methylene‐
cis
‐
p
‐menthane
A General Synthetic Method for the Preparation of Conjugated Dienes from Olefins Using Bromomethanesulfonyl Bromide: 1,2‐Dimethylenecyclohexane
Authors: Block Eric , Aslam Mohammad
Published: November 2003

A general synthetic method for the preparation of conjugated dienes from olefins using bromomethanesulfonyl bromide: 1,2‐dimethylenecyclohexane

intermediate: bromomethanesulfonyl bromide

intermediate: 1‐bromo‐1‐methyl‐2‐(bromomethylsulfonyl)cyclohexane (54.0 g, 0.16 mol) in tert‐butyl alcohol–tetrahydrofuran (9 : 1, 100 mL)

product: 1,2‐dimethylenecyclohexane

product: C
3
H
7
CHCHCHCH
2

product: C
5
H
11
CHCHCHCH
2

product: (E)‐C
3
H
7
CHCHC(C
4
H
9
)CH
2

product: (E)‐C
4
H
9
CHCHC(CH
3
)CH
2

product: (E)‐C
4
H
9
CHCHC(CH
3
)CH
2
 + CH
2
CHC(C
5
H
11
)CH
2

product: PhCHCHCHCH
2

product: PhOCHCHCHCH
2

product: HO(CH
2
)8CHCHCHCH
2

product: (CH3)3SiCHCHCHCH
2

product: CH
2
CH(CH
2
)5CHCHCHCH
2

product: CH
2
CHCHCH(CH
2
)4CHCHCHCH
2

product: (CH
3
)2Si(CHCHCHCH
2
)2
Preparation and Inverse‐Electron‐Demand
D
iels–
A
lder Reaction of an Electron‐Deficient Diene: Methyl 2‐Oxo‐5,6,7,8‐Tetrahydro‐2
H
‐1‐Benzopyran‐3‐Carboxylate and 6‐Methoxy‐7‐Methoxycarbonyl‐1,2,3,4‐Tetrahydronaphthalane
Authors: Boger Dale L. , Mullican Michael D.
Published: November 2003

Preparation and inverse‐electron‐demand Diels–Alder reaction of an electron‐deficient diene: methyl 2‐oxo‐5,6,7,8‐tetrahydro‐2
H
‐1‐benzopyran‐3‐carboxylate and 6‐methoxy‐7‐methoxycarbonyl‐1,2,3,4‐tetrahydronaphthalane

reactant: dimethyl methoxymethylenemalonate (8.1 g, 46 mmol, )

intermediate: methyl 2‐oxo‐5,6,7,8‐tetrahydro‐2H‐1‐benzopyran‐3‐carboxylate

reactant: 1,1‐Dimethoxyethylene (1.1 g, 12.5 mmol, )

product: 6‐methoxy‐7‐methoxycarbonyl‐1,2,3,4‐tetrahydronaphthalene
(S)‐(−)‐1‐Amino‐2‐Methoxymethylpyrrolidine (SAMP) and (R)‐(+)‐1‐Amino‐2‐Methoxymethylpyrrolidine (RAMP), Versatile Chiral Auxiliaries
Authors: Enders Dieter , Fey Peter , Kipphardt Helmut
Published: November 2003

(S)‐(−)‐1‐amino‐2‐methoxymethylpyrrolidine (SAMP) and (R)‐(+)‐1‐amino‐2‐methoxymethylpyrrolidine (RAMP), versatile chiral auxiliaries

product: (R)‐(+)‐1‐amino‐2‐methoxymethylpyrrolidine (RAMP)

intermediate: hydroxymethylpyrrolidine

intermediate: (S)‐(−)‐1‐formyl‐2‐hydroxymethylpyrrolidine.

intermediate: (S)‐(+)‐2‐methoxymethylpyrrolidine.

intermediate: (S)‐(−)‐1‐amino‐2‐methoxymethylpyrrolidine (SAMP)
(−)‐α‐pinene by isomerization of (−)‐β‐pinene
Authors: Brown Charles A. , Jadhav Prabhakav K.
Published: November 2003

(−)‐α‐pinene by isomerization of (−)‐β‐pinene

product: (−)‐α‐pinene
A General [3 + 2] Annulation:
cis
‐4‐
exo
‐Isopropenyl‐1,9‐dimethyl‐8‐(trimethylsilyl)bicyclo[4.3.0]non‐8‐en‐2‐one
Authors: Danheiser Rick L. , Fink David M. , Tsai Yeun‐Min
Published: November 2003

A general [3 + 2] annulation:
cis
‐4‐
exo
‐Isopropenyl‐1,9‐Dimethyl‐8‐(Trimethylsilyl)Bicyclo[4.3.0]non‐8‐en‐2‐one

product: cis‐4‐exo‐isopropenyl‐1,9‐dimethyl‐8‐(trimethylsilyl)bicyclo[4.3.0]non‐8‐en‐2‐one
(1‐oxo‐2‐propenyl)trimethylsilane
Authors: Danheiser Rick L. , Fink David M. , Okano Kazuo , Tsai Yeun‐Min , Szczepanski Steven W.
Published: November 2003

(1‐OXO‐2‐PROPENYL)TRIMETHYLSILANE

intermediate: (1‐hydroxy‐2‐propenyl)trimethylsilane

byproduct: 3‐tert‐butyl‐4‐hydroxy‐5‐methylphenyl sulfide

product: (1‐oxo‐2‐propenyl)trimethylsilane
α‐Unsubstituted γ,δ‐Unsaturated Aldehydes by
C
laisen Rearrangement: 3‐Phenyl‐4‐pentenal
Authors: Vogel Dennis E. , Büchi George H.
Published: November 2003

α‐Unsubstituted γ,δ‐unsaturated aldehydes by Claisen rearrangement: 3‐phenyl‐4‐pentenal

intermediate: (E)‐(carboxyvinyl)trimethylammonium betaine

intermediate: (E)‐3‐[(E)‐3‐phenyl‐2‐propenoxy]acrylic acid

product: 3‐phenyl‐4‐pentenal
Aprotic Double
M
ichael Addition: 1,3‐Dimethyl‐5‐Oxobicyclo[2.2.2]Octane‐2‐Carboxylic Acid
Authors: Spitzner Dietrich , Engler Anita
Published: November 2003

Aprotic double Michael addition: 1,3‐dimethyl‐5‐oxobicyclo[2.2.2]octane‐2‐carboxylic acid

intermediate: Methyl 1,3‐dimethyl‐5‐oxobicyclo[2.2.2]octane‐2‐carboxylate.

product: 1,3‐Dimethyl‐5‐oxobicyclo[2.2.2]octane‐2‐carboxylic acid.
Conjugate Addition–Cyclization of a Cyanocuprate: 2‐Carbomethoxy‐3‐Vinylcyclopentanone
Authors: Nugent William A. , Hobbs Frank W.
Published: November 2003

Conjugate addition–cyclization of a cyanocuprate: 2‐carbomethoxy‐3‐vinylcyclopentanone

intermediate: dimethyl (E)‐2‐hexenedioate

product: 2‐carbomethoxy‐3‐vinylcyclopentanone

byproduct: Tetramethyltin
Synthesis of Biaryls via Palladium‐Catalyzed Cross‐Coupling: 2‐Methyl‐4′‐Nitrobiphenyl
Authors: Negishi Ei‐Ichi , Takahashi Tamotsu , King Anthony O.
Published: November 2003

Synthesis of biaryls via palladium‐catalyzed cross‐coupling: 2‐methyl‐4′‐nitrobiphenyl

product: 2‐methyl‐4′‐nitrobiphenyl

unknown: mesitylzinc chloride

product: mesitylmagnesium bromide
Triple‐Bond Isomerizations: 2‐ to 9‐Decyn‐1‐ol
Authors: Abrams Suzanne R. , Shaw Angela C.
Published: November 2003

Triple‐Bond Isomerizations: 2‐ to 9‐decyn‐1‐ol

product: 9‐Decyn‐1‐ol (12.8–13.5 g, 83–88%)
Hofmann Rearrangement Under Mildly Acidic Conditions Using [I,I‐Bis(Trifluoroacetoxy)]Iodobenzene: Cyclobutylamine Hydrochloride from Cyclobutanecarboxamide
Authors: Almond Merrick R. , Stimmel Julie B. , Thompson E. Alan , Loudon G. Marc
Published: November 2003

Hofmann rearrangement under mildly acidic conditions using [I,I‐bis(trifluoroacetoxy)]iodobenzene: cyclobutylamine hydrochloride from cyclobutanecarboxamide

reactant: [I,I‐bis(trifluoroacetoxy)iodo]benzene (16.13 g, 37.5 mmol; ) in 37.5 mL of acetonitrile

intermediate: Cyclobutanecarboxamide (2.48 g, 25 mmol)

product: cyclobutylamine hydrochloride
Preparation and Inverse‐Electron‐Demand
D
iels–
A
lder Reaction of an Electron‐Deficient Heterocyclic Azadiene: Triethyl 1,2,4‐Triazine‐3,5,6‐Tricarboxylate and 2,3,6‐Tricarboethoxypyridine
Authors: Boger Dale L. , Panek James S. , Yasuda Masami
Published: November 2003

Preparation and inverse‐electron‐demand Diels–Alder reaction of an electron‐deficient heterocyclic azadiene: triethyl 1,2,4‐triazine‐3,5,6‐tricarboxylate and 2,3,6‐tricarboethoxypyridine

intermediate: ethyl thioamidooxalate

intermediate: ethyl oxalamidrazonate

reactant: diethyl dioxosuccinate

product: triethyl 1,2,4‐triazine‐3,5,6‐tricarboxylate
(
S
)‐2‐Chloroalkanoic Acids of High Enantiomeric Purity from (
S
)‐2‐Amino Acids: (
S
)‐2‐Chloropropanoic Acid
Authors: Koppenhoefer Bernhard , Schurig Volker
Published: November 2003

(
S
)‐2‐Chloroalkanoic acids of high enantiomeric purity from (
S
)‐2‐amino acids: (
S
)‐2‐chloropropanoic acid

product: (S)‐2‐chloropropanoic acid

product: (2R,3S)‐2‐chloro‐3‐methylpentanoic acid

product: CH3

product: CH(CH3)2

product: CH2CH(CH3)2

product: (3S)‐CH(CH3)CH2CH3
(
R
)‐Alkyloxiranes of High Enantiomeric Purity from (
S
)‐2‐Chloroalkanoic Acids via (
S
)‐2‐Chloro‐1‐Alkanols: (
R
)‐Methyloxirane
Authors: Koppenhoefer Bernhard , Schurig Volker
Published: November 2003

(
R
)‐Alkyloxiranes of high enantiomeric purity from (
S
)‐2‐chloroalkanoic acids via (
S
)‐2‐chloro‐1‐alkanols: (
R
)‐methyloxirane

intermediate: (S)‐2‐Chloropropan‐1‐ol.

product: (R)‐Methyloxirane

unknown: S)‐methyloxirane
Utilization of β‐Chloro Alkylidene/Arylidene Malonates in Organic Synthesis: Ethyl Cyclopropylpropiolate
Authors: Hormi Osmo
Published: November 2003

Utilization of β‐chloro alkylidene/arylidene malonates in organic synthesis: ethyl cyclopropylpropiolate

reactant: 166 g (0.73 mol) of diethyl cyclopropylcarbonylmalonate

intermediate: diethyl 2‐chloro‐2‐cyclopropylethene‐1,1‐dicarboxylate

product: Ethyl cyclopropylpropiolate
6‐Diethylphosphonomethyl‐2,2‐dimethyl‐1,3‐dioxen‐4‐one
Authors: Boeckman Robert K. , Perni Robert B. , Macdonald James E. , Thomas Anthony J.
Published: November 2003

6‐Diethylphosphonomethyl‐2,2‐dimethyl‐1,3‐dioxen‐4‐one

intermediate: 6‐Chloromethyl‐2,2‐dimethyl‐1,3‐dioxen‐4‐one.

product: 6‐diethylphosphonomethyl‐2,2‐dimethyl‐1,3‐dioxen‐4‐one
Addition of Dialkylamines to Myrcene:
N,N
‐Diethylgeranylamine
Authors: Takabe Kunihiko , Katagiri Takao , Tanaka Juntaro , Fujita Tsutomu , Watanabe Shoji , Suga Kyoichi
Published: November 2003

Addition of dialkylamines to myrcene:
N,N
‐diethylgeranylamine

reactant: 13.60 g (74 mmol) of myrcene

product: 91.2–92.5% of
N,N
‐diethylgeranylamine

product:
N,N
‐dipropylgeranylamine
N
‐
tert
‐Butoxycarbonyl‐
L
‐Leucinal
Authors: Goel O. P. , Krolls U. , Stier M. , Kesten S.
Published: November 2003

N
‐
tert
‐butoxycarbonyl‐
L
‐leucinal

product:
N
‐
tert
‐Butoxycarbonyl‐
L
‐leucinal: Boc‐
L
‐leucinal

intermediate: Boc‐
L
‐leucine
N
‐methyl‐O‐methycarboxamide
Condensation of (−)‐Dimenthyl Succinate Dianion with 1,ω‐Dihalides: (+)‐(1
S
,2
S
)‐Cyclopropane‐1,2‐Dicarboxylic Acid
Authors: Furuta Kyoji , Iwanaga Kiyoshi , Yamamoto Hisashi
Published: November 2003

Condensation of (−)‐dimenthyl succinate dianion with 1,ω‐dihalides: (+)‐(1
S
,2
S
)‐cyclopropane‐1,2‐dicarboxylic acid

intermediate: (−)‐dimenthyl succinate

intermediate: (−)‐dimenthyl (1
S
,2
S
)‐cyclopropane‐1,2‐dicarboxylate

product: (+)‐(1
S
,2
S
)‐cyclopropane‐1,2‐dicarboxylic acid
Palladium‐Catalyzed Coupling of Acid Chlorides with Organotin Reagents: Ethyl (E)‐4‐(4‐Nitrophenyl)‐4‐Oxo‐2‐Butenoate
Authors: Renaldo A. F. , Labadie J. W. , Stille J. K.
Published: November 2003

Palladium‐catalyzed coupling of acid chlorides with organotin reagents: Ethyl (E)‐4‐(4‐nitrophenyl)‐4‐oxo‐2‐butenoate

reactant: 70.7 g (0.22 mol) of tributyltin chloride

intermediate: tributylethynylstannane

reactant: 23.1 g (0.079 mol) of tributyltin hydride

intermediate: (E)‐1,2‐bis(tributylstannyl)ethylene

intermediate: ethyl (E)‐3‐(tributylstannyl)propenoate

product: ethyl (E)‐4‐(4‐nitrophenyl)‐4‐oxo‐2‐butenoate

byproduct: ethyl (Z)‐3‐(tributylstannyl)propenoate
4,4‐Dimethyl‐2‐Cyclopenten‐1‐one
Authors: Pauley David , Anderson Frank , Hudlicky Tomas
Published: November 2003

4,4‐Dimethyl‐2‐cyclopenten‐1‐one

intermediate: 165.1 g (1.29 mol) 2,2‐dimethyl‐4‐oxopentanal

product: 4,4‐dimethyl‐2‐cyclopenten‐1‐one
Alkylations Using Hexacarbonyl(Propargylium)Dicobalt Salts: 2‐(1‐Methyl‐2‐Propynyl)Cyclohexanone
Authors: Varghese Valsamma , Saha Manasi , Nicholas Kenneth M.
Published: November 2003

Alkylations using hexacarbonyl(propargylium)dicobalt salts: 2‐(1‐methyl‐2‐propynyl)cyclohexanone

solvent: 300 mL of dry dimethylformamide

intermediate: 1‐trimethylsiloxycyclohexene

reactant: hexacarbonyl(1‐methyl‐2‐propynylium)dicobalt tetrafluoroborate

product: 2‐(1‐methyl‐2‐propynyl)cyclohexanone
Dienophile Activation via Selenosulfonation: 1‐(Phenylsulfonyl)cyclopentene
Authors: Lin Ho‐Shen , Coghlan Michael J. , Paquette Leo A.
Published: November 2003

Dienophile activation via selenosulfonation: 1‐(phenylsulfonyl)cyclopentene

intermediate: phenyl benzeneselenosulfonate

product: 1‐(Phenylsulfonyl)cyclopentene.
Selective Cyclopropanation of (
S
)‐(−)‐Perillyl Alcohol: 1‐Hydroxymethyl‐4‐(1‐methylcyclopropyl)‐1‐cyclohexene
Authors: Maruoka Keiji , Sakane Soichi , Yamamoto Hisashi
Published: November 2003

Selective cyclopropanation of (
S
)‐(−)‐perillyl alcohol: 1‐Hydroxymethyl‐4‐(1‐methylcyclopropyl)‐1‐cyclohexene

product: 1‐hydroxymethyl‐4‐(1‐methylcyclopropyl)‐1‐cyclohexene

product: decylcyclopropane
Trimethylsilyldiazomethane
Authors: Shioiri Takayuki , Aoyama Toyohiko , Mori Shigehiro
Published: November 2003

Trimethylsilyldiazomethane

reactant: 91.2 g (0.33 mol) of diphenyl phosphorazidate

product: trimethylsilyldiazomethane
Yeast Reduction of 2,2‐Dimethylcyclohexane‐1,3‐dione: (
S
)‐(+)‐3‐Hydroxy‐2,2‐dimethylcyclohexanone)
Authors: Mori Kenji , Mori Hideto
Published: November 2003

Yeast reduction of 2,2‐dimethylcyclohexane‐1,3‐dione: (
S
)‐(+)‐3‐hydroxy‐2,2‐dimethylcyclohexanone)

intermediate: 2,2‐dimethylcyclohexane‐1,3‐dione

product: (
S
)‐3‐hydroxy‐2,2‐dimethylcyclohexanone
(
S
)‐4‐(phenylmethyl)‐2‐oxazolidinone
Authors: Gage James R. , Evans David A.
Published: November 2003

(
S
)‐4‐(Phenylmethyl)‐2‐oxazolidinone

intermediate: (S)‐Phenylalanol

product: (S)‐4‐(Phenylmethyl)‐2‐oxazolidinone
Allylic Acetoxylation of Cycloalkenes: 2‐Cyclohepten‐1‐yl Acetate
Authors: Heumann A. , Åkermark B. , Hansson S. , Rein T.
Published: November 2003

Allylic acetoxylation of cycloalkenes: 2‐cyclohepten‐1‐yl acetate

product: 2‐cyclohepten‐1‐yl acetate
Transesterification of Methyl Esters of Aromatic and α,β‐Unsaturated Acids with Bulky Alcohols: (−)‐Menthyl Cinnamate and (−)‐Menthyl Nicotinate
Authors: Meth‐Cohn Otto
Published: November 2003

Transesterification of methyl esters of aromatic and α,β‐unsaturated acids with bulky alcohols: (−)‐menthyl cinnamate and (−)‐menthyl nicotinate

product: (1R)‐(−)‐Menthyl cinnamate

product: (1R)‐(−)‐Menthyl nicotinate
3‐Methyl‐2(5
H
)‐furanone
Authors: Näsman Jan H.
Published: November 2003

3‐Methyl‐2(5
H
)‐furanone

intermediate: 2(5
H
)‐Furanone.

intermediate: Furyl phosphorodichloridate.

intermediate: Furyl
N,N,N
′,
N
′‐tetramethyldiamidophosphate

product: 3‐Methyl‐2(5
H
)‐furanone.

reactant: 10.9 g (50 mmol) of furyl tetramethyldiamidophosphate

intermediate: 2‐(3‐methylfuryl) tetramethyldiamidophosphate

solvent: diisopropyl ether/hexane
Iminium Ion‐Based
D
iels–
A
lder Reactions:
N
‐Benzyl‐2‐Azanorbornene
Authors: Grieco Paul A. , Larsen Scott D.
Published: November 2003

Iminium ion‐based Diels–Alder reactions:
N
‐benzyl‐2‐azanorbornene

product:
N
‐benzyl‐2‐azanorbornene

product: 2‐azanorbornene

product: 2‐azanorbornen‐3‐one

product: 2‐azanorbornene
The
C
arroll Rearrangement: 5‐Dodecen‐2‐one
Authors: Wilson Stephen R. , Augelli Corinne E.
Published: November 2003

The Carroll rearrangement: 5‐dodecen‐2‐one

intermediate: (1‐Ethenyl)heptanyl 3‐ketobutanoate.

reactant: 3‐Hydroxy‐1‐nonene (, 7.5 g, 0.053 mol)

intermediate: 2‐Carboxy‐5‐dodecen‐2‐one.

product: 5‐Dodecen‐2‐one.
IntramolecularOxidative Coupling of a Bisenolate: 4‐Methyltricyclo[2.2.2.0
3,5
]Octane‐2,6‐dione
Authors: Poupart Marc‐André , Lassalle Gilbert , Paquette Leo A.
Published: November 2003

Intramolecular oxidative coupling of a bisenolate: 4‐methyltricyclo[2.2.2.0
3,5
]octane‐2,6‐dione

intermediate: 3‐Methylcyclohexanone‐3‐acetic acid.

intermediate: 4‐Methylbicyclo[2.2.2]octane‐2,6‐dione.

product: 4‐Methyltricyclo[2.2.2.03,5]octane‐3,5‐dione.
p
‐
tert
‐Butylcalix[4]arene
Authors: Gutsche C. D. , Iqbal M.
Published: November 2003

p
‐
tert
‐Butylcalix[4]arene

reactant:
p
‐
tert
‐Butylphenol from Aldrich Chemical Company, Inc.

product:
p
‐
tert
‐butylcalix[4]arene
Diasteroselective Formation of α‐Methoxycarbonyl Lactones Through an Intramolecular
D
iels–
A
lder Reaction: (4
RS
,4a
RS
,6
RS
,8a
RS
)‐, (4
S
,4a
S
,6
S
,8a
S
)‐ and (4
R
,4a
R
,6
R
,8a
R
)‐4‐Methoxycarbonyl‐1,1,6‐trimethyl‐1,4,4A,5,6,7,8,8a‐octahydro‐2,3‐benzopyrone [
rac
‐5, (+)‐5, and (−)‐5]
Authors: Tietze L. F. , Kiedrowski G. v. , Fahlbusch K.‐G. , Voss E.
Published: November 2003

Diasteroselective formation of α‐methoxycarbonyl lactones through an intramolecular Diels–Alder reaction: (4
RS
,4a
RS
,6
RS
,8a
RS
)‐, (4
S
,4a
S
,6
S
,8a
S
)‐ and (4
R
,4a
R
,6
R
,8a
R
)‐4‐methoxycarbonyl‐1,1,6‐trimethyl‐1,4,4A,5,6,7,8,8a‐octahydro‐2,3‐benzopyrone [
rac
‐5, (+)‐5, and (−)‐5]

product: (4RS,4aRS,6RS,8aRS)‐, (4S,4aS,6S,8aS)‐ and (4R,4aR,6R,8aR)‐4‐methoxycarbonyl‐1,1,6‐trimethyl‐1,4,4A,5,6,7,8,8a‐octahydro‐2,3‐benzopyrone [rac‐5, (+)‐5, and (−)‐5]

intermediate: Diels–Alder‐adduct rac‐3

catalyst: ethylenediammonium diacetate (EDDA) (, 500 mg, 2.77 mmol)

reactant: (S)‐citronellal

reactant: (R)‐citronellal
Asymmetric Synthesis of 4,4‐Dialkylcyclohexenones from Chiral Bicyclic Lactams: (
R
)‐4‐Ethyl‐4‐allyl‐2‐cyclohexen‐1‐one
Authors: Meyers Albert I. , Berney Daniel
Published: November 2003

Asymmetric Synthesis of 4,4‐dialkylcyclohexenones from chiral bicyclic lactams: (
R
)‐4‐ethyl‐4‐allyl‐2‐cyclohexen‐1‐one

intermediate: Hexahydro‐3‐(hydroxymethyl)‐8a‐methyl‐2‐phenyl[2S,3S,8aR]‐5‐oxo‐5H‐oxazolo[3,2‐a]pyridine (Bicyclic lactam)

reactant: (1S,2S)‐(+)‐2‐amino‐1‐phenyl‐1,3‐propanediol (32.4 g, 194 mmol)

intermediate: Hexahydro‐6‐ethyl‐3‐(hydroxymethyl)‐6‐allyl‐2‐phenyl[2S,3S,6S,8aR]‐5‐oxo‐5H‐oxazolo[3,2‐a]pyridine

product: (R)‐4‐Ethyl‐4‐allyl‐2‐cyclohexen‐1‐one
NucleophilicHydroxymethylation by the (Isopropoxydimethylsilyl)methyl
G
rignard Reagent: 1‐(Hydroxymethyl)cyclohexanol from Cyclohexanone
Authors: Tamao Kohei , Ishida Neyoshi , Ito Yoshihiko , Kumada Makoto
Published: November 2003

Nucleophilic hydroxymethylation by the (isopropoxydimethylsilyl)methyl Grignard reagent: 1‐(hydroxymethyl)cyclohexanol from cyclohexanone

reactant: (isopropoxydimethylsilyl)methyl chloride (16.67 g, 100 mmol)

intermediate: 1‐[(isopropoxydimethylsilyl)methyl]cyclohexanol

product: 1‐(hydroxymethyl)cyclohexanol
(−)‐
D
‐2,10‐Camphorsultam
Authors: Weismiller Michael C. , Towson James C. , Davis Franklin A.
Published: November 2003

(−)‐D‐2,10‐camphorsultam

product: (−)‐2,10‐camphorsultam
(+)‐(2
R
,8a
S
)‐10‐(Camphorylsulfonyl)Oxaziridine
Authors: Towson James C. , Weismiller Michael C. , Lal G. Sankar , Sheppard Aurelia C. , Kumar Anil , Davis Franklin A.
Published: November 2003

(+)‐(2
R
,8a
S
)‐10‐(camphorylsulfonyl)oxaziridine

intermediate: (+)‐(1S)‐10‐Camphorsulfonamide

intermediate: (−)‐(camphorsulfonyl)imine

product: (+)‐(2R, 8aS)‐10‐Camphorylsulfonyloxaziridine

product: (−)‐(2S,8aR)‐10‐(camphorylsulfonyl)oxaziridine
Methyl (
Z
)‐3‐(Phenylsulfonyl)Prop‐2‐enoate
Authors: Hirst G. C. , Parsons P. J.
Published: November 2003

Methyl (
Z
)‐3‐(Phenylsulfonyl)Prop‐2‐enoate

product: methyl (E)‐3‐(phenylsulfonyl)prop‐2‐enoate

product: methyl (Z)‐3‐(phenylsulfonyl)prop‐2‐enoate
A General Synthetic Method for the Oxidation of Primary Alcohols to Aldehydes: (
S
)‐(+)‐2‐Methylbutanal
Authors: Anelli Pier Lucio , Montanari Fernando , Quici Silvio
Published: November 2003

A General synthetic method for the oxidation of primary alcohols to aldehydes: (
S
)‐(+)‐2‐methylbutanal

reactant: 44.05 g (0.50 mol) of (S)‐(−)‐2‐methyl‐1‐butanol

product: (S)‐(+)‐2‐methylbutanal

byproduct: (S)‐(+)‐2‐Methylbutanoic acid

product: butanal
9‐
n
‐Butyl‐1,2,3,4,5,6,7,8‐Octahydroacridin‐4‐ol
Authors: Bell Thomas W. , Cho Young‐Moon , Firestone Albert , Healy Karin , Liu Jia , Ludwig Richard , Rothenberger Scott D.
Published: November 2003

9‐
n
‐Butyl‐1,2,3,4,5,6,7,8‐octahydroacridin‐4‐ol

intermediate: 8‐n‐butyl‐2‐hydroxytricyclo[7.3.1.02,7]tridecan‐13‐one

intermediate: 9‐n‐Butyl‐1,2,3,4,5,6,7,8‐octahydroacridine.

intermediate: 9‐n‐butyl‐1,2,3,4,5,6,7,8‐octahydroacridine‐N‐oxide

product: 9‐n‐butyl‐1,2,3,4,5,6,7,8‐octahydroacridin‐4‐ol
Synthesis of Alkyl Propanoates by a Haloform Reaction of a Trichloro Ketone: Ethyl 3,3‐Diethoxypropanoate
Authors: Tietze L. F. , Voss E. , Hartfiel U.
Published: November 2003

Synthesis of alkyl propanoates by a haloform reaction of a trichloro ketone: ethyl 3,3‐diethoxypropanoate

intermediate: 1,1,1‐Trichloro‐4‐ethoxy‐3‐buten‐2‐one (4)

reactant: trichloroacetyl chloride, 2 (173 g, 0.96 mol)

product: Ethyl 3,3‐diethoxypropanoate (5)
N‐tert‐Butoxycarbonyl‐
L
‐Serine β‐Lactone and (S)‐3‐Amino‐2‐Oxetanone p‐Toluenesulfonic Acid Salt
Authors: Pansare Sunil V. , Arnold Lee D. , Vederas John C.
Published: November 2003

N‐tert‐butoxycarbonyl‐L‐serine β‐lactone and (S)‐3‐amino‐2‐oxetanone p‐toluenesulfonic acid salt

reactant: diethyl azodicarboxylate (DEAD) (27.86 g, 160 mmol)

intermediate: N‐(tert‐butoxycarbonyl)‐L‐serine β‐lactone

reactant: p‐toluenesulfonic acid (13.5 g, 78.5 mmol)

reactant: trifluoroacetic acid (200 mL)

product: (S)‐3‐amino‐2‐oxetanone p‐toluenesulfonic acid salt

reactant: Dimethyl azodicarboxylate (17.7 mL)
N‐(Benzyloxycarbonyl)‐
L
‐Vinylglycine Methyl Ester
Authors: Carrasco Michael , Jones Robert J. , Kamel Scott , Rapoport H. , Truong Thien
Published: November 2003

N‐(benzyloxycarbonyl)‐
L
‐vinylglycine methyl ester

intermediate: N‐(Benzyloxycarbonyl)‐L‐methionine methyl ester (2)

reactant: L‐methionine methyl ester hydrochloride (117.6 g, 0.56 mol)

intermediate: Methyl L‐2‐(benzyloxycarbonylamino)‐4‐(methylsulfinyl)butanoate (3)

product: N‐(Benzyloxycarbonyl)‐L‐vinylglycine methyl ester (4)
(S)‐(−)‐ and (R)‐(+)‐1,1′‐Bi‐2‐Naphthol
Authors: Kazlauskas Romas J.
Published: November 2003

(S)‐(−)‐ and (R)‐(+)‐1,1′‐bi‐2‐naphthol

product: (S)‐(−)‐1,1′‐Bi‐2‐naphthol

product: (R)‐(+)‐1,1′‐Bi‐2‐naphthol

intermediate: (R)‐binaphthol dipentanoate
9‐Thiabicyclo[3.3.1]Nonane‐2,6‐dione
Authors: Bishop Roger
Published: November 2003

9‐Thiabicyclo[3.3.1]nonane‐2,6‐dione

intermediate: (1α,2α,5α,6α)‐2,6‐Dichloro‐9‐thiabicyclo[3.3.1]nonane (1)

intermediate: (endo,endo)‐9‐Thiabicyclo[3.3.1]nonane‐2,6‐diol (2)

product: 9‐Thiabicyclo[3.3.1]nonane‐2,6‐dione (3)

reactant: sulfur dichloride
Substitution Reactions of 2‐Benzenesulfonyl Cyclic Ethers: Tetrahydro‐2‐(Phenylethynyl)‐2H‐Pyran
Authors: Brown Dearg S. , Ley Steven V.
Published: November 2003

Substitution reactions of 2‐benzenesulfonyl cyclic ethers: tetrahydro‐2‐(phenylethynyl)‐2H‐pyran

product: tetrahydro‐2‐(phenylethynyl)‐2H‐pyran
Tris(Trimethylsilyl)Silane
Authors: Dickhaut Joachim , Giese Bernd
Published: November 2003

Tris(trimethylsilyl)silane

product: Tris(trimethylsilyl)silane 1

reactant: tributylstannane
Cyclopropanation Using an Iron‐Containing Methylene Transfer Reagent: 1,1‐Diphenylcyclopropane
Authors: Mattson Matthew N. , O'Connor Edward J. , Helquist Paul
Published: November 2003

Cyclopropanation using an iron‐containing methylene transfer reagent: 1,1‐diphenylcyclopropane

reactant: cyclopentadienyliron dicarbonyl dimer [C5H5(CO)2Fe]2, (0.50 mol equiv, 0.21 mol, 74.4 g; and )

intermediate: (η5‐C5H5)(CO)2FeCH2S+(CH3)2BF4−

product: 1,1‐diphenylcyclopropane

solvent: nitromethane
Spiroannelation via Organobis(Cuprates): 9,9‐Dimethylspiro[4.5]Decan‐7‐One
Authors: Wender Paul A. , White Alan W. , McDonald Frank E.
Published: November 2003

Spiroannelation via organobis(cuprates): 9,9‐dimethylspiro[4.5]decan‐7‐one

intermediate: 3‐chloro‐5,5‐dimethylcyclohex‐2‐en‐1‐one

product: 9,9‐dimethylspiro[4.5]decan‐7‐one
Alkynyl(Phenyl)Iodonium Tosylates: Preparation and Stereospecific Coupling with Vinylcopper Reagents. Formation of Conjugated Enynes. 1‐Hexynyl(Phenyl)Iodonium Tosylate and (E)‐5‐Phenyldodec‐5‐En‐7‐Yne
Authors: Stang Peter J. , Kitamura Tsugio
Published: November 2003

Alkynyl(phenyl)iodonium tosylates: preparation and stereospecific coupling with vinylcopper reagents. formation of conjugated enynes. 1‐hexynyl(phenyl)iodonium tosylate and (E)‐5‐phenyldodec‐5‐en‐7‐yne

intermediate: 1‐trimethylsilyl‐1‐hexyne

product: (E)‐5‐Phenyldodec‐5‐en‐7‐yne

product: 1‐hexynyl(phenyl)iodonium tosylate

product: CH
3
CCIPh·OTs

product: EtCCIPh·OTs

product: N‐PrCCIPh·OTs

product: Me
3
SiCCIPh·OTs

product: PhCCIPh·OTs

product: t‐BuCCIPh·OTs
(E,Z)‐1‐Methoxy‐2‐Methyl‐3‐(Trimethylsiloxy)‐1,3‐Pentadiene
Authors: Myles David C. , Bigham Mathew H.
Published: November 2003

(E,Z)‐1‐methoxy‐2‐methyl‐3‐(trimethylsiloxy)‐1,3‐pentadiene

intermediate: 114 g (1.0 mol) of 1‐hydroxy‐2‐methylpent‐1‐en‐3‐one

intermediate: 96 g (0.75 mol) of 1‐methoxy‐2‐methylpent‐1‐en‐3‐one

product: 1‐methoxy‐2‐methyl‐3‐(trimethylsiloxy)‐1,3‐pentadiene
Nickel‐Catalyzed Silylolefination of Allylic Dithioacetals: (E,E)‐Trimethyl(4‐Phenyl‐1,3‐Butadienyl)Silane
Authors: Ni Zhi‐Jie , Luh Tien‐Yau
Published: November 2003

Nickel‐catalyzed silylolefination of allylic dithioacetals: (E,E)‐trimethyl(4‐phenyl‐1,3‐butadienyl)silane

intermediate: 2‐(2‐Phenylethenyl)‐1,3‐dithiolane

intermediate: (Trimethylsilyl)methylmagnesium chloride

intermediate: (E,E)‐Trimethyl(4‐phenyl‐1,3‐butadienyl)silane
α‐Acetylenic Esters from α‐Acylmethylenephosphoranes: Ethyl 4,4,4‐Trifluorotetrolate
Authors: Hamper B. C.
Published: November 2003

α‐Acetylenic esters from α‐acylmethylenephosphoranes: ethyl 4,4,4‐trifluorotetrolate

intermediate: ethyl 4,4,4‐trifluoro‐2‐(triphenylphosphoranylidene)acetoacetate

product: ethyl 4,4,4‐trifluorotetrolate
(1R,2R)‐(+)‐ and (1S,2S)‐(−)‐ 1,2‐Diphenyl‐1,2‐Ethylenediamine
Authors: Pikul S. , Corey E. J.
Published: November 2003

(1R,2R)‐(+)‐ and (1S,2S)‐(−)‐ 1,2‐diphenyl‐1,2‐ethylenediamine

intermediate: 2,2‐Spirocyclohexane‐4,5‐diphenyl‐2H‐imidazole

intermediate: (±)‐1,2‐Diphenyl‐1,2‐ethylenediamine

product: (1S,2S)‐(−)‐ and (1R,2R)‐(+)‐1,2‐Diphenyl‐1,2‐ethylenediamine

product: (S,S)‐(−)‐diamine

product: (R,R)‐diamine
Synthesis of 2‐Substituted Naphthalenediol Derivatives using Chromium Carbene Complexes: 1‐Acetoxy‐2‐Butyl‐4‐Methoxynaphthalene
Authors: Timko Joseph M. , Yamashita Ayako
Published: November 2003

Synthesis of 2‐substituted naphthalenediol derivatives using chromium carbene complexes: 1‐acetoxy‐2‐butyl‐4‐methoxynaphthalene

unknown: 20.0 g (64.0 mmol) of pentacarbonyl[phenyl(methoxy)chromium]carbene

product: 1‐acetoxy‐2‐butyl‐4‐methoxynaphthalene
A Hydroxymethyl Anion Equivalent: Tributyl[(Methoxymethoxy)Methyl]Stannane
Authors: Danheiser Rick L. , Romines Karen R. , Koyama Hiroo , Gee Stephen K. , Johnson Carl R. , Medich John R.
Published: November 2003

A hydroxymethyl anion equivalent: tributyl[(methoxymethoxy)methyl]stannane

intermediate: (tributylstannyl)methanol

reactant: Boron trifluoride etherate (13.0 mL, 0.106 mol)

product: tributyl[(methoxymethoxy)methyl]stannane
Preparation and use of (Methoxymethoxy)Methyllithium: 1‐(Hydroxymethyl)Cycloheptanol
Authors: Johnson Carl R. , Medich John R. , Danheiser Rick L. , Romines Karen R. , Koyama Hiroo , Gee Stephen K.
Published: November 2003

Preparation and use of (methoxymethoxy)methyllithium: 1‐(hydroxymethyl)cycloheptanol

intermediate: 1‐[(methoxymethoxy)methyl]cycloheptanol

product: 1‐[hydroxymethyl)cycloheptanol
Ethyl 1‐Naphthylacetate: Ester Homologation via Ynolate Anions
Authors: Reddy Rajarathnam E. , Kowalski Conrad J.
Published: November 2003

Ethyl 1‐naphthylacetate: ester homologation via ynolate anions

product: ethyl 1‐naphthylacetate
Inverse Electron‐Demand
D
iels‐
A
lderCycloaddition of a Ketene Dithioacetal. Copper Hydride‐Promoted Reduction of a Conjugated Enone. 9‐Dithiolanobicyclo[3.2.2]Non‐6‐En‐2‐One from Tropone
Authors: Dahnke Karl R. , Paquette Leo A.
Published: November 2003

Inverse electron‐demand Diels‐Alder cycloaddition of a ketene dithioacetal. Copper hydride‐promoted reduction of a conjugated enone. 9‐dithiolanobicyclo[3.2.2]non‐6‐en‐2‐one from tropone

intermediate: tropone

intermediate: 9‐dithiolanobicyclo[3.2.2]nona‐3,6‐dien‐2‐one

product: 9‐Dithiolanobicyclo[3.2.2]non‐6‐en‐2‐one
A Selective, Heterogeneous Oxidation Using A Mixture of Potassium Permanganate and Cupric Sulfate: (3as,7ar)‐Hexahydro‐(3S,6R)‐Dimethyl‐2(3H)‐Benzofuranone
Authors: Jefford Charles W. , Li Yun , Wang Ying
Published: November 2003

A selective, heterogeneous oxidation using a mixture of potassium permanganate and cupric sulfate: (3aS,7aR)‐hexahydro‐(3S,6R)‐dimethyl‐2(3H)‐benzofuranone

reactant: 31 g (0.20 mol) of isopulegol

intermediate: (−)‐(1R,3R,4S,8R)‐p‐menthane‐3,9‐diol

product: 3aS,7aR‐hexahydro‐3S,6R‐dimethyl‐2(3H)‐benzofuranone
9‐Bromo‐9‐Phenylfluorene
Authors: Jamison T. F. , Lubell W. D. , Dener J. M. , Krisché M. J. , Rapoport H.
Published: November 2003

9‐Bromo‐9‐phenylfluorene

product: 9‐bromo‐9‐phenylfluorene

intermediate: 9‐phenyl‐9‐fluorenol
(S)‐N‐(9‐Phenylfluoren‐9‐yl)Alanine and (S)‐Dimethyl N‐(9‐Phenylfluoren‐9‐yl)Aspartate
Authors: Jamison T. F. , Rapoport H.
Published: November 2003

(S)‐N‐(9‐phenylfluoren‐9‐yl)alanine and (S)‐dimethyl N‐(9‐phenylfluoren‐9‐yl)aspartate

product: (S)‐N‐(9‐Phenylfluoren‐9‐yl)alanine (2)

reactant: L‐alanine (1, 13.5 g, 150 mmol,)

product: (S)‐Dimethyl N‐(9‐phenylfluoren‐9‐yl)aspartate (4)

byproduct: 9‐methoxy‐9‐phenylfluorene (5.30 g, 19.5 mmol,)

byproduct: 9‐phenyl‐9‐fluorenol (2.00 g, 7.7 mmol,)

reactant: (S)‐Dimethyl aspartate hydrochloride
D‐(R)‐Glyceraldehyde Acetonide
Authors: Schmid Christopher R. , Bryant Jerry D.
Published: November 2003

D‐(R)‐glyceraldehyde acetonide

product: 2,3‐O‐isopropylidene‐D‐glyceraldehyde

intermediate: 1,2:5,6‐diisopropylidene‐D‐mannitol
(3S,4S)‐3‐Amino‐1‐(3,4‐Dimethoxybenzyl)‐4‐[(R)‐2,2‐Dimethyl‐1,3‐Dioxolan‐4‐yl]‐2‐Azetidinone
Authors: Hubschwerlen Christian , Specklin Jean‐Luc
Published: November 2003

(3S,4S)‐3‐amino‐1‐(3,4‐dimethoxybenzyl)‐4‐[(R)‐2,2‐dimethyl‐1,3‐dioxolan‐4‐yl]‐2‐azetidinone

intermediate: 100 g of phthalylglycyl chloride (90% based on phthalylglycine)

product: (3S,4S)‐3‐amino‐1‐(3,4‐dimethoxybenzyl)‐4‐[(R)‐2,2‐dimethyl‐1,3‐dioxolan‐4‐yl]‐2‐azetidinone

intermediate: N‐[(2R,3R)‐cis‐1‐(3,4‐Dimethoxybenzyl)‐2‐[(S)‐2,2‐dimethyl‐1,3‐dioxolan‐4‐yl]‐4‐oxo‐3‐azetidinyl]phthalimide
(1R,5R)‐(+)‐Verbenone of High Optical Purity
Authors: Sivik Mark R. , Stanton Kenetha J. , Paquette Leo A.
Published: November 2003

(1R,5R)‐(+)‐verbenone of high optical purity

reactant: (1R)‐(+)‐α‐Pinene (25.0 g, 0.183 mol

intermediate: mixture of acetates

product: verbenone
Chiral (Acyloxy)Borane Complex‐Catalyzed Asymmetric
D
iels‐
A
lder Reaction: (1R)‐1,3,4‐Trimethyl‐3‐Cyclohexene‐1‐Carboxaldehyde
Authors: Furuta Kyoji , Gao Qing‐Zhi , Yamamoto Hisashi
Published: November 2003

Chiral (acyloxy)borane complex‐catalyzed asymmetric Diels‐Alder reaction: (1R)‐1,3,4‐trimethyl‐3‐cyclohexene‐1‐carboxaldehyde

intermediate: (−)‐dibenzyl tartrate

intermediate: dibenzyl mono(2,6‐dimethoxybenzoyl)tartrate

intermediate: mono(2,6‐dimethoxybenozyl)tartaric acid

product: (1R)‐1,3,4‐trimethyl‐3‐cyclohexene‐1‐carboxaldehyde
Rearrangement of trans‐Stilbene Oxide to Diphenylacetaldehyde with Catalytic Methylaluminum bis(4‐Bromo‐2,6‐Di‐tert‐Butylphenoxide)
Authors: Ooi Takashi , Maruoka Keiji , Yamamoto Hisashi
Published: November 2003

Rearrangement of trans‐stilbene oxide to diphenylacetaldehyde with catalytic methylaluminum bis(4‐bromo‐2,6‐di‐tert‐butylphenoxide)

intermediate: 4‐bromo‐2,6‐di‐tert‐butylphenol

product: diphenylacetaldehyde

byproduct: Tischenko product
Synthesis of Functionalized Enynes by Palladium/Copper‐Catalyzed Coupling Reactions of Acetylenes with (Z)‐2,3‐Dibromopropenoic acid Ethyl Ester: (Z)‐2‐Bromo‐5‐(Trimethylsilyl)‐2‐Penten‐4‐ynoic Acid Ethyl Ester
Authors: Myers Andrew G. , Dragovich Peter S.
Published: November 2003

Synthesis of functionalized enynes by palladium/copper‐catalyzed coupling reactions of acetylenes with (Z)‐2,3‐dibromopropenoic acid ethyl ester: (Z)‐2‐bromo‐5‐(trimethylsilyl)‐2‐penten‐4‐ynoic acid ethyl ester

intermediate: (Z)‐2,3‐dibromo‐2‐propenoic acid ethyl ester

byproduct: bis(trimethylsilyl)butadiyne

product: (Z)‐2‐Bromo‐5‐(trimethylsilyl)‐2‐penten‐4‐ynoic acid ethyl ester

byproduct: (E)‐2‐[(trimethylsilyl)ethynyl]‐5‐(trimethylsilyl)‐2‐penten‐4‐ynoic acid ethyl ester
7‐Methoxyphthalide
Authors: Wang X. , de Silva S. O. , Reed J. N. , Billadeau R. , Griffen E. J. , Chan A. , Snieckus V.
Published: November 2003

7‐Methoxyphthalide

intermediate: N,N‐diethyl‐2‐methoxybenzamide

intermediate: N,N‐Diethyl‐2‐formyl‐6‐methoxybenzamide

product: 7‐methoxyphthalide
A Water‐Soluble Tin Hydride: Tris[3‐(2‐Methoxyethoxy)Propyl]Stannane
Authors: Light James , Breslow Ronald
Published: November 2003

A water‐soluble tin hydride: tris[3‐(2‐methoxyethoxy)propyl]stannane

intermediate: 3‐(2‐Methoxyethoxy)propene (1)

intermediate: 1‐Bromo‐3‐(2‐methoxyethoxy)propane (2)

intermediate: Tetra[3‐(2‐methoxyethoxy)propyl]stannane (3)

intermediate: Bromotris[3‐(2‐methoxyethoxy)propyl]stannane (4)

intermediate: Tris[3‐(2‐methoxyethoxy)propyl]stannane (5)
Reaction of Sulfoxides with Diethylaminosulfur Trifluoride: Fluoromethyl Phenyl Sulfone, A Reagent for the Synthesis of Fluoroalkenes
Authors: McCarthy James R. , Matthews Donald P. , Paolini John P.
Published: November 2003

Reaction of sulfoxides with diethylaminosulfur trifluoride: fluoromethyl phenyl sulfone, a reagent for the synthesis of fluoroalkenes

intermediate: fluoromethyl phenyl sulfide 1

product: fluoromethyl phenyl sulfone (2)
(3,3‐Difluoroallyl)Trimethylsilane
Authors: Gonzalez Javier , Foti Matthew J. , Elsheimer Seth
Published: November 2003

(3,3‐difluoroallyl)trimethylsilane

reactant: dibromodifluoromethane (83.9 g, 36.5 mL, 0.4 mol)

intermediate: (1,3‐dibromo‐3,3‐difluoropropyl)trimethylsilane (78.3 g, 0.25 mol)

intermediate: 3‐bromo‐3,3‐difluoropropyltrimethylsilane

product: (3,3‐difluoroallyl)trimethylsilane
Stereoselective Synthesis of 2,2‐Disubstituted 1‐Fluoro‐Alkenes: (E)‐[[Fluoro(2‐Phenylcyclohexylidene)‐Methyl]Sulfonyl]Benzene and (Z)‐[2‐(Fluoromethylene)‐Cyclohexyl]Benzene
Authors: McCarthy James R. , Matthews Donald P. , Paolini John P.
Published: November 2003

Stereoselective synthesis of 2,2‐disubstituted 1‐fluoro‐alkenes: (E)‐[[fluoro(2‐phenylcyclohexylidene)‐methyl]sulfonyl]benzene and (Z)‐[2‐(fluoromethylene)‐cyclohexyl]benzene

product: (E)‐[[Fluoro(2‐phenylcyclohexylidene)methyl]sulfonyl]benzene (1)

reactant: diethyl chlorophosphate (24.8 g, 0.14 mol)

intermediate: (E)‐Tributyl[fluoro(2‐phenylcyclohexylidene)methyl]stannane (2)

product: (Z)‐[2‐(Fluoromethylene)cyclohexyl]benzene (3)
Phenylthioacetylene
Authors: Magriotis Plato A. , Brown John T.
Published: November 2003

Phenylthioacetylene

intermediate: phenylthio‐1,2‐dibromoethane

intermediate: 1‐bromovinyl phenyl sulfide

product: phenylthioacetylene
3‐[(1S)‐1,2‐Dihydroxyethyl]‐1,5‐Dihydro‐3H‐2,4‐Benzodioxepine
Authors: Oi Ryu , Sharpless K. Barry
Published: November 2003

3‐[(1S)‐1,2‐dihydroxyethyl]‐1,5‐dihydro‐3H‐2,4‐benzodioxepine

intermediate: 1,2‐benzenedimethanol

intermediate: 3‐vinyl‐1,5‐dihydro‐3H‐2,4‐benzodioxepine

catalyst: dihydroquinidine 9‐O‐(9′‐phenanthryl) ether and, [0.75 g, (1.5 mmol, 1 mol%, 0.0057 M in the organic phase)]

product: 3‐[(1S)‐1,2‐dihydroxyethyl)]‐1,5‐dihydro‐3H‐2,4‐benzodioxepine
(1R,5S)‐(−)‐6,6‐Dimethyl‐3‐Oxabicyclo[3.1.0]Hexan‐2‐One. Highly Enantioselective Intramolecular Cyclopropanation Catalyzed by Dirhodium(II) Tetrakis[Methyl 2‐Pyrrolidone‐5(R)‐Carboxylate]
Authors: Doyle Michael P. , Winchester William R. , Protopopova Marina N. , Kazala Amy P. , Westrum Larry J.
Published: November 2003

(1R,5S)‐(−)‐6,6‐dimethyl‐3‐oxabicyclo[3.1.0]hexan‐2‐one. Highly enantioselective intramolecular cyclopropanation catalyzed by dirhodium(II) tetrakis[methyl 2‐pyrrolidone‐5(R)‐carboxylate]

intermediate: (−)‐Methyl 2‐pyrrolidone‐5(R)‐carboxylate

intermediate: (+)‐Dirhodium(II) tetrakis[methyl 2‐pyrrolidone‐5(R)‐carboxylate]

intermediate: 3‐Methyl‐2‐buten‐1‐yl acetoacetate

intermediate: 3‐Methyl‐2‐buten‐1‐yl diazoacetate

product: (1R,5S)‐(−)‐6,6‐Dimethyl‐3‐oxabicyclo[3.1.0]hexan‐2‐one

reactant: (R)‐(+)‐2‐Pyrrolidone‐5‐carboxylic acid [Fluka Chemika‐BioChemika, D‐pyroglutamic acid,

$[\alpha]^{22}_{\rm D}$

+9 ± 1° (H
2
O, c 5)]
EnantioselectiveHydrolysis of cis‐3,5‐Diacetoxycyclopentene: (1R,4S)‐(+)‐4‐Hydroxy‐2‐Cyclopentenyl Acetate
Authors: Deardorff Donald R. , Windham Colin Q. , Craney Chris L.
Published: November 2003

Enantioselective hydrolysis of cis‐3,5‐diacetoxycyclopentene: (1R,4S)‐(+)‐4‐hydroxy‐2‐cyclopentenyl acetate

reactant: 16.70 g (118 mmol) of (±)‐cis‐4‐acetoxy‐1‐hydroxycyclopent‐2‐ene [(±)‐1]

intermediate: cis‐3,5‐diacetoxycyclopentene (2)

product: (1R,4S)‐(+)‐4‐hydroxy‐2‐cyclopentenyl acetate [(+)‐1]
(4R)‐(+)‐tert‐Butyldimethylsiloxy‐2‐Cyclopenten‐1‐one
Authors: Paquette Leo A. , Earle Martyn J. , Smith Graham F.
Published: November 2003

(4R)‐(+)‐tert‐Butyldimethylsiloxy‐2‐Cyclopenten‐1‐one

reactant: 23 g (162 mmol) of (1R,4S)‐(+)‐4‐hydroxy‐2‐cyclopentenyl acetate

solvent: petroleum ether

intermediate: (4R)‐(+)‐acetoxy‐2‐cyclopenten‐1‐one

intermediate: 7.7 g (78 mmol) of (4R)‐(+)‐hydroxy‐2‐cyclopenten‐1‐one

product: (4R)‐(+)‐tert‐butyldimethylsiloxy‐2‐cyclopenten‐1‐one
Synthesis of β‐Lactones and Alkenes via Thiol Esters: (E)‐2,3‐Dimethyl‐3‐Dodecene
Authors: Danheiser Rick L. , Nowick James S. , Lee Janette H. , Miller Raymond F. , Huboux Alexandre H.
Published: November 2003

Synthesis of β‐lactones and alkenes via thiol esters: (E)‐2,3‐dimethyl‐3‐dodecene

reactant: 45.0 g (0.17 mol) of S‐phenyl decanoate

intermediate: β‐lactone

product: (E)‐2,3‐dimethyl‐3‐dodecene

solvent: petroleum ether (Mallinkrodt Inc., bp 35–60°C)
Regio‐ and StereoselectiveIntramolecularHydrosilylation of α‐Hydroxy Enol Ethers: 2,3‐syn‐2‐Methoxymethoxy‐1,3‐Nonanediol
Authors: Tamao Kohei , Nakagawa Yoshiki , Ito Yoshihiko
Published: November 2003

Regio‐ and stereoselective intramolecular hydrosilylation of α‐hydroxy enol ethers: 2,3‐syn‐2‐methoxymethoxy‐1,3‐nonanediol

intermediate: 2‐Bromoethyl methoxymethyl ether

intermediate: Methoxymethyl vinyl ether

intermediate: 2‐Methoxymethoxy‐1‐nonen‐3‐ol.

product: 2‐Methoxymethoxy‐1,3‐nonanediol
A General Procedure for
M
itsunobu Inversion of Sterically Hindered Alcohols: Inversion of Menthol. (1S,2S,5R)‐5‐Methyl‐2‐(1‐Methylethyl)Cyclohexyl 4‐Nitrobenzoate
Authors: Dodge Jeffrey A. , Nissen Jeffrey S. , Presnell Misti
Published: November 2003

A General procedure for Mitsunobu inversion of sterically hindered alcohols: inversion of menthol. (1S,2S,5R)‐5‐methyl‐2‐(1‐methylethyl)cyclohexyl 4‐nitrobenzoate

product: (1S,2S,5R)‐5‐Methyl‐2‐(1‐methylethyl)cyclohexyl 4‐nitrobenzoate
Detrifluoroacetylative Diazo Group Transfer: (E)‐1‐Diazo‐4‐Phenyl‐3‐Buten‐2‐One
Authors: Danheiser Rick L. , Miller Raymond F. , Brisbois Ronald G.
Published: November 2003

Detrifluoroacetylative diazo group transfer: (E)‐1‐diazo‐4‐phenyl‐3‐buten‐2‐one

product: (E)‐1‐diazo‐4‐phenyl‐3‐buten‐2‐one

product: α‐diazoacetophenone