Asymmetric synthesis of pyrrolidinoindolines. Application for the practical total synthesis of (-)-phenserine

被引：180

作者：

Huang, A ^{[1
]}

Kodanko, JJ ^{[1
]}

Overman, LE ^{[1
]}

机构：

[1] Univ Calif Irvine, Dept Chem, Irvine, CA 92697 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2004年 / 126卷 / 43期

关键词：

D O I：

10.1021/ja046690e

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A versatile route to enantiopure 3,3-disubstituted oxindoles and 3a-substituted pyrrolidinoindolines is described in which diastereoselective dialkylation of enantiopure ditriflate 10 with oxindole enolates is the central step. These reactions are rare examples of alkylations of prostereogenic enolates with chiral sp(3) electrophiles that proceed with high facial selectivity (10-20:1). The scope of this method is explored, and a model to rationalize the sense of stereoselection is advanced. This dialkylation chemistry was used to synthesize (-)-phenserine on a multigram scale in six steps and 43% overall yield from 5-methoxy-1,3-dimethyloxindole (27) and to complete a short formal total synthesis of (-)-physostigmine (2).

引用

收藏

页码：14043 / 14053

页数：11

相关论文

共 74 条

[11] BROMO-SUBSTITUTED PHYSOSTIGMINE ALKALOIDS FROM A MARINE BRYOZOA FLUSTRA-FOLIACEA [J].

CARLE, JS ;

CHRISTOPHERSEN, C .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1979, 101 (14) :4012-4013

[12] MARINE ALKALOIDS .2. BROMO ALKALOIDS FROM THE MARINE BRYOZOAN FLUSTRA-FOLIACEA - ISOLATION AND STRUCTURE ELUCIDATION [J].

CARLE, JS ;

CHRISTOPHERSEN, C .

JOURNAL OF ORGANIC CHEMISTRY, 1980, 45 (09) :1586-1589

[13]

Cassel S, 2001, EUR J ORG CHEM, V2001, P875

[14]

Corey EJ, 1998, ANGEW CHEM INT EDIT, V37, P388, DOI 10.1002/(SICI)1521-3773(19980302)37:4<388::AID-ANIE388>3.0.CO

[15]

2-V

[16] A NEW EFFICIENT AND MILD SYNTHESIS OF 2-OXINDOLES BY ONE-POT WOLFF-KISHNER LIKE REDUCTION OF ISATIN DERIVATIVES [J].

CRESTINI, C ;

SALADINO, R .

SYNTHETIC COMMUNICATIONS, 1994, 24 (20) :2835-2841

[17] Catalytic asymmetric synthesis of all-carbon quaternary stereocenters [J].

Douglas, CJ ;

Overman, LE .

PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2004, 101 (15) :5363-5367

[18] Catalytic asymmetric synthesis of quaternary carbons bearing two aryl substituents. Enantioselective synthesis of 3-alkyl-3-aryl oxindoles by catalytic asymmetric intramolecular Heck reactions [J].

Dounay, AB ;

Hatanaka, K ;

Kodanko, JJ ;

Oestreich, M ;

Overman, LE ;

Pfeifer, LA ;

Weiss, MM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (20) :6261-6271

[19] ON ENANTIOMORPH-POLARITY ESTIMATION [J].

FLACK, HD .

ACTA CRYSTALLOGRAPHICA SECTION A, 1983, 39 (NOV) :876-881

[20] Enantioselective creation of quaternary carbon centers through addition-elimination reaction: Asymmetric nitroolefination of 3-substituted 2-oxindoles [J].

Fuji, K ;

Kawabata, T ;

Ohmori, T ;

Shang, MH ;

Node, M .

HETEROCYCLES, 1998, 47 (02) :951-964

← 1 2 3 4 5 6 7 8 →