FORMAL TOTAL SYNTHESIS OF DESERPIDINE DEMONSTRATING A VERSATILE AMINO-CLAISEN REARRANGEMENT WENKERT CYCLIZATION STRATEGY FOR THE PREPARATION OF FUNCTIONALIZED YOHIMBANE RING-SYSTEMS

被引：44

作者：

BAXTER, EW ^{[1
]}

LABAREE, D ^{[1
]}

AMMON, HL ^{[1
]}

MARIANO, PS ^{[1
]}

机构：

[1] UNIV MARYLAND,DEPT CHEM & BIOCHEM,COLLEGE PK,MD 20742

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1990年 / 112卷 / 21期

关键词：

D O I：

10.1021/ja00177a032

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A strategy for the synthesis of the functionally complex yohimbane, deserpidine, based upon a combination of zwitterionic amino-Claisen rearrangement and Wenkert cyclization methodologies is presented. Key elements in this plan include (1) the construction of the intermediate N-tryptophylisoquinuclidene 7-ketal 19 and its transformation with tert-butyl propiclate to the N-tryptophylhydroisoquinoline enone 22, (2) stereocontrolled introduction of the E-ring C-16 ester, C-17 methoxyl, and C-18 benzoate functionality, and (3) Wenkert cyclization of the N-tryptophyltetrahydronicotinate containing intermediate 30 to produce the yohimbane 39. A formal total synthesis of deserpidine is then accomplished by preparation of the isodeserpidine related C-18-alcohol 42, an advanced intermediate in Szantay's previous total synthesis of this target. © 1990, American Chemical Society. All rights reserved.

引用

页码：7682 / 7692

页数：11

共 70 条

[1] MODEL STUDIES PROBING THE AMINO-CLAISEN REARRANGEMENT APPROACH TO HYDROISOQUINOLINE SYNTHESIS - DEVELOPMENT OF METHODS FOR STEREOCONTROLLED INTRODUCTION OF RESERPINE-E RING-TYPE FUNCTIONALITY [J].