A quantum chemical exploration of the Horner-Wadsworth-Emmons reaction

被引：50

作者：

Brandt, P ^{[1
]}

Norrby, PO

Martin, I

Rein, T

机构：

[1] Royal Inst Technol, Dept Chem, S-10044 Stockholm, Sweden

[2] Royal Danish Sch Pharm, Dept Med Chem, DK-2100 Copenhagen, Denmark

[3] Inst Chem, Dept Bioorgan Chem, EE-0026 Tallinn, Estonia

[4] Tech Univ Denmark, Dept Organ Chem, DK-2800 Lyngby, Denmark

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1998年 / 63卷 / 04期

关键词：

D O I：

10.1021/jo971973t

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The mechanism of the Horner-Wadsworth-Emmons (HWE) reaction has been investigated using high level quantum mechanical calculations on a realistic model system. The salvation contribution has been evaluated using the PCM/DIR method. In the free, anionic system, the rate-determining step was found to be the ring closure of an oxyanion to an oxaphosphetane. Solvation was found to have a drastic influence an the reaction path. In most solvated systems, the bimolecular formation of the oxyanion intermediate may be rate limiting. Previously postulated isomerization side paths were investigated. Several effects that could rationalize experimentally observed trends far (E)/(Z)-selectivities have been identified.

引用

页码：1280 / 1289

页数：10

共 75 条

[1] The asymmetric Horner-Emmons reaction using a benzopyrano-isoxazolidine auxiliary [J].