From Silylated Trishomoallylic Alcohols to Dioxaspiroundecanes or Oxocanes: Catalyst and Substitution Influence

被引：20

作者：

Barbero, Asuncion ^{[1
]}

Diez-Varga, Alberto ^{[1
]}

Herrero, Manuel ^{[1
]}

Pulido, Francisco J. ^{[1
]}

机构：

[1] Univ Valladolid, Fac Ciencias, Dept Quim Organ, Campus Miguel Delibes, E-47011 Valladolid, Spain

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2016年 / 81卷 / 07期

关键词：

PRINS CYCLIZATION; RING-FORMATION; ALPHA; BETA-UNSATURATED NITRILES; STEREOSELECTIVE-SYNTHESIS; ALLYLSILYL ALCOHOLS; SAKURAI REACTION; DERIVATIVES; EPOXIDES; ALLENE; VINYLSTANNANES;

D O I：

10.1021/acs.joc.5b02260

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A versatile method for the synthesis of dioxaspiroundecanes through a tandem Sakurai-Prins cyclization of allylsilyl alcohols in the presence of TMSOTf is described. The process is general and highly stereoselective with total control in the creation of three new stereogenic centers in a single step. Moreover, a very interesting chemoselectivity has been observed depending on the nature of the catalyst used or the substitution of the trishomoallylic alcohol, since the same reaction under BF3 center dot OEt2 catalysis or using alcohols with allylic substituents provides exclusively the corresponding oxocanes, by a direct silyl-Prins cyclization.

引用

页码：2704 / 2712

页数：9

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