In Situ-Generated Iodonium Ylides as Safe Carbene Precursors for the Chemoselective Intramolecular Buchner Reaction

被引：34

作者：

Mo, Shanyan ^{[1
]}

Li, Xinhao ^{[1
]}

Xu, Jiaxi ^{[1
]}

机构：

[1] Beijing Univ Chem Technol, State Key Lab Chem Resource Engn, Dept Organ Chem, Fac Sci, Beijing 100029, Peoples R China

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2014年 / 79卷 / 19期

基金：

中国国家自然科学基金;

关键词：

CYCLOPROPANATION; ENANTIOSELECTIVITY; AZIRIDINATION; REAGENTS; MALONATE;

D O I：

10.1021/jo501628h

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A chemoselective intramolecular Buchner reaction employing iodonium ylides as safe carbene precursors has been developed. Iodonium ylides are generated in situ from N-benzyl-2-cyanoacetamides and PhI(OAc)(2) in the presence of base and undergo intramolecular Buchner reaction under catalysis from Cu(OAc)(2 center dot)H2O, affording fused cyclohepta-1,3,5-triene derivatives in up to 85% yield. The N,N-dibenzyl-2-cyanoacetamides with two different benzyl groups undergo intramolecular Buchner reaction on their electron-rich benzyl groups selectively. The reaction is not sensitive to air and moisture and uses a safe alternative version of the corresponding diazo starting materials. The overall transformation involving the carbene pathway has been verified.

引用

页码：9186 / 9195

页数：10

共 47 条

[1] Versatile synthesis of 4-spiro-β-lactam-3-carbonitriles via the intramolecular nucleophilic cyclization of N-(p-hydroxyphenyl) cyanoacetamides [J].