Malonic Acid Half Oxyesters and Thioesters: Solvent-Free Synthesis and DFT Analysis of Their Enols

被引：8

作者：

Bew, Sean P. ^{[1
]}

Stephenson, G. Richard ^{[1
]}

Rouden, Jacques ^{[2
]}

Martinez-Lozano, Luis A. ^{[1
]}

Seylani, Haseena ^{[1
]}

机构：

[1] Univ E Anglia, Sch Chem, Norwich NR4 7TJ, Norfolk, England

[2] ENSICAEN, CNRS, UMR 6507, LCMT, F-14050 Caen, France

来源：

ORGANIC LETTERS | 2013年 / 15卷 / 15期

基金：

英国工程与自然科学研究理事会;

关键词：

ENANTIOSELECTIVE DECARBOXYLATIVE ADDITION; POLYKETIDE SYNTHASES; ALDOL REACTIONS; BIOSYNTHESIS; CONVENIENT; CONDENSATION; MECHANISM; ACYLATION; MIMICRY; ESTERS;

D O I：

10.1021/ol400804b

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A much improved synthetic route to malonic acid half thioesters (MAHTs) and oxyesters (MAHOs), the easy incorporation of deuterium labeling expecially in MAHTs, and an unexpectedly large difference in enolization chemistry between MAHTs and MAHOs are reported. Density functional theory calculations explore the origins of this difference and identify an additional MAHT molecular orbital which increases delocalization between sulfur and the enol in both cisoid and transoid forms.

引用

页码：3805 / 3807

页数：3

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