Cyclic Guanidine Organic Catalysts: What Is Magic About Triazabicyclodecene?

被引：177

作者：

Kiesewetter, Matthew K. ^{[2
]}

Scholten, Marc D. ^{[2
]}

Kirn, Nicole ^{[2
]}

Weber, Ryan L. ^{[2
]}

Hedrick, James L. ^{[1
]}

Waymouth, Robert M. ^{[2
]}

机构：

[1] IBM Corp, Almaden Res Ctr, San Jose, CA 95120 USA

[2] Stanford Univ, Dept Chem, Stanford, CA 94305 USA

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2009年 / 74卷 / 24期

关键词：

RING-OPENING POLYMERIZATION; N-HETEROCYCLIC CARBENES; TRANSESTERIFICATION REACTIONS; HYDROGEN-BOND; ZWITTERIONIC POLYMERIZATION; ASYMMETRIC-SYNTHESIS; BICYCLIC GUANIDINE; PHOSPHAZENE BASES; DIETHYL CARBONATE; ESTERS;

D O I：

10.1021/jo902369g

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The bicyclic guanidine 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) is an effective organocatalyst for the formation of amides from esters and primary amines. Mechanistic and kinetic investigations support a nucleophilic mechanism where TBD reacts reversibly with esters to generate an acyl-TBD intermediate that acylates amines to generate the amides. Comparative investigations of the analogous bicyclic guanidine 1,4,6-triazabicyclo[3.3.0]oct-4-ene (TBO) reveal it to be a much less active acylation catalyst than TBD. Theoretical and mechanistic Studies imply that the higher reactivity of TBD is a consequence of both its higher basicity and nucleophilicity than TBO as well as the high reactivity of the acyl-TBD intermediate, which is sterically prevented from adopting a planar amide structure.

引用

页码：9490 / 9496

页数：7

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