1,3-DIPOLAR CYCLOADDITIONS TO BAYLIS-HILLMAN ADDUCTS - RATIONALE FOR THE OBSERVED DIASTEREOSELECTIVITY

被引：52

作者：

ANNUNZIATA, R ^{[1
]}

BENAGLIA, M ^{[1
]}

CINQUINI, M ^{[1
]}

COZZI, F ^{[1
]}

RAIMONDI, L ^{[1
]}

机构：

[1] DIPARTIMENTO CHIM ORGAN & IND,I-20133 MILAN,ITALY

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1995年 / 60卷 / 15期

关键词：

D O I：

10.1021/jo00120a009

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Diazomethane and benzonitrile oxide cycloadditions were performed on Baylis-Hillman adducts derived from methyl acrylate and aldehydes (beta'-alkoxy-alpha,beta-unsaturated esters). The reactions proceed in good chemical yields, and their stereochemical outcome can be explained by the ''inside alkoxy effect'' theory. In the case of diazomethane cycloadditions, however, electrostatic factors play a reduced role in comparison to the corresponding nitrile oxide reactions, while steric effects are of major importance in governing the stereoselectivity. This different behavior of the two 1,3-dipoles finds a rationale in the analysis of the atomic charges as calculated at the RHF/3-21G level of theory for the transition structure of these reactions.

引用

页码：4697 / 4706

页数：10

共 32 条

[11] COMPLETE PROTON AND C-13 NMR ASSIGNMENT OF THE ALKALOID GEPHYROTOXIN THROUGH THE USE OF HOMONUCLEAR HARTMANN-HAHN AND TWO-DIMENSIONAL NMR-SPECTROSCOPY [J].