Synthesis of Enantiopure 3-Hydroxypiperidines from Sulfinyl Dienyl Amines by Diastereoselective Intramolecular Cyclization and [2,3]-Sigmatropic Rearrangement

被引：14

作者：

Simal, Carmen ^{[1
]}

Bates, Robert H. ^{[1
]}

Urena, Mercedes ^{[1
]}

Gimenez, Irene ^{[1
]}

Koutsou, Christina ^{[1
]}

Infantes, Lourdes ^{[2
]}

Fernandez de la Pradilla, Roberto ^{[1
]}

Viso, Alma ^{[1
]}

机构：

[1] CSIC, Inst Quim Organ Gen, E-28006 Madrid, Spain

[2] CSIC, Inst Quim Fis Rocasolano, E-28006 Madrid, Spain

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2015年 / 80卷 / 15期

关键词：

DIRECTED ENANTIOSELECTIVE SYNTHESIS; AZA-MICHAEL REACTION; DIELS-ALDER REACTIONS; STEREOSELECTIVE-SYNTHESIS; ASYMMETRIC-SYNTHESIS; ALLYLIC SULFOXIDES; 3-SUBSTITUTED PIPERIDINES; SUBSTITUTED PIPERIDINES; ABSOLUTE-CONFIGURATION; 4+2 CYCLOADDITIONS;

D O I：

10.1021/acs.joc.5b01307

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The highly diastereoselective base-promoted intramolecular cyclization of a variety of enantiopure sulfinyl dienyl amines provides novel sulfinyl tetrahydropyridines that are readily converted to 3-hydroxy tetrahydropyridines via sigmatropic rearrangement. The influence of N- and C- substituents on the process has been studied. Procedures to shorten the sequence such as the tandem cyclization followed by [2,3] -sigmatropic rearrangement, as well as cyclization of the free amine, under Boc- or ArSO- deprotection conditions have been examined. Good to excellent levels of selectivity are generally observed for the reported transformations (dr: 75/25 to >98/2). A novel protocol to access substituted amino dienyl sulfoxides is also reported.

引用

页码：7674 / 7692

页数：19

共 98 条

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