Evidence for the Cyclic CN2 Carbene in Solution

被引：6

作者：

Hanzlova, Eva ^{[1
]}

Navratil, Rafael ^{[1
]}

Cejka, Jan ^{[1
]}

Boehm, Stanislav ^{[1
]}

Martinu, Tomas ^{[1
]}

机构：

[1] Inst Chem Technol, Dept Organ Chem, Prague 16628, Czech Republic

来源：

ORGANIC LETTERS | 2014年 / 16卷 / 03期

关键词：

N-HETEROCYCLIC CARBENES; AB-INITIO; ULTRAVIOLET-SPECTRA; DIAZIRINYL ANION; MATRIX-ISOLATION; STABILITY; PRECURSORS;

D O I：

10.1021/ol4036243

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Diazirinylidene (c-CN2) is formally the simplest of the N-heterocyclic carbenes. The intermediacy of this elusive species in the fragmentation of butyl 3-bromodiazirine-3-carboxylate (la) with pent-4-en-1-ols and their sodium alkoxides in DMF is supported by the formation of 2-oxabicyclo[4.1.0]heptanes and dipentenoxymethanes. These products result from an intramolecular [2 + 1] cycloaddition and O-H insertion, respectively, of pentenoxymethylenes suggested to originate from the reaction of the electrophilic c-CN2 with an alkoxide ion. The reaction of la with primary or secondary amines in methanol affords the corresponding 3-bromodiazirine-3-carboxamides.

引用

页码：852 / 855

页数：4