General Approach to Enantiopure 1-Aminopyrrolizidines: Application to the Asymmetric Synthesis of the Loline Alkaloids

被引：1

作者：

Davies, Stephen G. ^{[1
]}

Fletcher, Ai M. ^{[1
]}

Linsdall, Sean M. ^{[1
]}

Roberts, Paul M. ^{[1
]}

Thomson, James E. ^{[1
]}

机构：

[1] Univ Oxford, Dept Chem, Chem Res Lab, Oxford OX1 3TA, England

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2023年 / 88卷 / 13期

关键词：

STEREOSELECTIVE-SYNTHESIS; AMINO-ACID; (+)-LOLINE;

D O I：

10.1021/acs.joc.3c00047

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The synthesis of a range of loline alkaloids is reported.The C(7)and C(7a) stereogenic centers for the targets were formed by the establishedconjugate addition of lithium (S)-N-benzyl-N-(alpha-methylbenzyl)amide to tert-butyl 5-benzyloxypent-2-enoate, ensuing enolate oxidationto give an alpha-hydroxy-beta-amino ester, and then formal exchangeof the resultant amino and hydroxyl functionalities (via the intermediacyof the corresponding aziridinium ion) to give an alpha-amino-beta-hydroxyester. Subsequent transformation gave a 3-hydroxyprolinal derivativewhich was converted to the corresponding N-tert-butylsulfinylimine. Mannich-type reaction with theenolate derived from O-Boc protected methyl glycolatethen formed the remaining C(1) and C(2) stereogenic centers for thetargets. The 2,7-ether bridge was formed by a displacement reaction,completing construction of the loline alkaloid core. Facile manipulationsthen gave a range of loline alkaloids, including loline itself.

引用

页码：8093 / 8098

页数：6

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