Solvent-Dependent Divergent Functions of Sc(OTf)3 in Stereoselective Epoxide-Opening Spiroketalizations

被引：22

作者：

Sharma, Indrajeet ^{[1
]}

Wurst, Jacqueline M. ^{[2
,3
]}

Tan, Derek S. ^{[1
,2
,3
]}

机构：

[1] Mem Sloan Kettering Canc Ctr, Mol Pharmacol & Chem Program, New York, NY 10065 USA

[2] Mem Sloan Kettering Canc Ctr, Triinst PhD Program Chem Biol, New York, NY 10065 USA

[3] Mem Sloan Kettering Canc Ctr, Triinst Res Program, New York, NY 10065 USA

来源：

ORGANIC LETTERS | 2014年 / 16卷 / 09期

关键词：

AGENT PAPULACANDIN-D; BERKELIC ACID; NATURAL-PRODUCTS; FORMAL SYNTHESIS; STEREOCONTROLLED SYNTHESIS; KINETIC SPIROCYCLIZATION; EXPEDITIOUS SYNTHESIS; (-)-BERKELIC ACID; HUMAN TELOMERASE; GLYCAL EPOXIDES;

D O I：

10.1021/ol500853q

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A stereocontrolled synthesis of benzannulated spiroketals has been developed using solvent-dependent Sc(OTf)(3)-mediated spirocyclizations of exo-glycal epoxides having alcohol side chains. In THF, the reaction proceeds via Lewis acid catalysis under kinetic control with inversion of configuration at the anomeric carbon. In contrast, in CH2Cl2, Bronsted acid catalysis under thermodynamic control leads to retention of configuration. The reactions accommodate a variety of aryl substituents and ring sizes and provide stereochemically diverse spiroketals.

引用

页码：2474 / 2477

页数：4

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