Diastereoselective Additions of Allylmagnesium Reagents to α-Substituted Ketones When Stereochemical Models Cannot Be Used

被引：8

作者：

Bartolo, Nicole D. ^{[1
]}

Demkiw, Krystyna M. ^{[1
]}

Valentin, Elizabeth M. ^{[2
]}

Hu, Chunhua T. ^{[1
]}

Arabi, Alya A. ^{[3
,4
]}

Woerpel, K. A. ^{[1
]}

机构：

[1] NYU, Dept Chem, New York, NY 10003 USA

[2] St Marys Coll Calif, Moraga, CA 94575 USA

[3] United Arab Emirates Univ, Coll Med & Hlth Sci, Biochem Dept, Al Ain, U Arab Emirates

[4] UCL, Ctr Computat Sci, London WC1H 0AJ, England

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2021年 / 86卷 / 10期

基金：

美国国家卫生研究院; 美国国家科学基金会;

关键词：

PI-FACIAL DIASTEREOSELECTIVITY; NUCLEAR-MAGNETIC-RESONANCE; CHIRAL CARBONYL-COMPOUNDS; CONFORMATIONAL-ANALYSIS; GRIGNARD-REAGENTS; NUCLEOPHILIC ADDITIONS; ASYMMETRIC INDUCTION; AMBIDENT REACTIVITY; HALIDES; TEMPERATURE;

D O I：

10.1021/acs.joc.1c00553

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The stereoselectivities of reactions of allylmagnesium reagents with chiral ketones cannot be easily explained by stereochemical models. Competition experiments indicate that the complexation step is not reversible, so nucleophiles cannot access the widest range of possible encounter complexes and therefore cannot be analyzed easily using available models. Nevertheless, additions of allylmagnesium reagents to a ketone can still be stereoselective provided that the carbonyl group adopts a conformation that leads to one face being completely blocked from the approach of the allylmagnesium reagent.

引用

页码：7203 / 7217

页数：15

共 81 条

[11] Erosion of Stereochemical Control with Increasing Nucleophilicity: O-Glycosylation at the Diffusion Limit [J].