[3,3]-Sigmatropic Rearrangement/Allylboration/Cyclization Sequence: Enantioenriched Seven-Membered-Ring Carbamates and Ring Contraction to Pyrrolidines

被引：18

作者：

Mace, Aurelie ^{[1
]}

Touchet, Sabrina ^{[1
]}

Andres, Patricia ^{[1
]}

Cossio, Fernando ^{[2
,3
]}

Dorcet, Vincent ^{[1
]}

Carreaux, Francois ^{[1
]}

Carboni, Bertrand ^{[1
]}

机构：

[1] Univ Rennes 1, CNRS, UMR 6226, Inst Sci Chim Rennes, F-35042 Rennes, France

[2] Univ Basque Country, Fac Quim, Dept Quim Organ 1, San Sebastian 20018, Donostia, Spain

[3] DIPC, San Sebastian 20018, Donostia, Spain

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2016年 / 55卷 / 03期

关键词：

allylic compounds; asymmetric synthesis; heterocycles; reaction mechanisms; rearrangements; VERSATILE BUILDING-BLOCKS; INTERMOLECULAR ADDITION-REACTIONS; STEREOSELECTIVE-SYNTHESIS; HOMOALLYLIC ALCOHOLS; ASYMMETRIC-SYNTHESIS; DERIVATIVES; AMINO; INHIBITORS; ARYLATION; IONS;

D O I：

10.1002/anie.201509824

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The combination of in situ generated -isocyanato allylboronic esters and aldehydes afforded seven-membered-ring enecarbamates with high levels of diastereo- and enantiocontrol. They were easily converted into diversely substituted 1,3-oxazepan-2-ones. An unprecedented rearrangement of 5-acetoxy-7-aryl or styryl derivatives led to tetrasubstituted pyrrolidines. A computational study provides evidence on the feasibility of the proposed mechanism of this unusual ring contraction.

引用

页码：1025 / 1029

页数：5

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