Stereoselective Synthesis of 2,4,5-Trisubstituted Piperidines via Radical Cyclization

被引：12

作者：

Ragoussi, Maria-Eleni ^{[1
]}

Walker, Stephen M. ^{[1
]}

Piccanello, Andrea ^{[1
]}

Kariuki, Benson M. ^{[1
]}

Horton, Peter N. ^{[2
]}

Spencer, Neil ^{[1
]}

Snaith, John S. ^{[1
]}

机构：

[1] Univ Birmingham, Sch Chem, Birmingham B15 2TT, W Midlands, England

[2] Univ Southampton, Sch Chem, EPSRC Natl Crystallog Serv, Southampton SO17 1BJ, Hants, England

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2010年 / 75卷 / 21期

关键词：

ASYMMETRIC TOTAL-SYNTHESIS; WADSWORTH-EMMONS REACTION; 1ST TOTAL-SYNTHESIS; 2,4-DISUBSTITUTED PIPERIDINES; 4+2 ANNULATION; CARBONYL ENE; ESTERS; CASCADE; VINCADIFFORMINE; REARRANGEMENT;

D O I：

10.1021/jo101631y

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A novel approach to 2,4,5-trisubstituted piperidines is reported, involving the 6-exo cyclization of stabilized radicals onto alpha,beta-unsaturated esters. Only two of the four possible diastereoisomers are observed, with diastereomeric ratios ranging from 3:2 to 40:1 when the radical stabilizing group is vinyl or phenyl. Cyclization of a (triethylsilyl)vinyl-stabilized radical gives the corresponding piperidine radical as a single diastereoisomer that may either be trapped by tributyltin hydride to afford the 2,4,5-trisubstituted piperidine or undergo a second 5-endo cyclization onto the (triethylsilyl)vinyl substituent to produce the 3,5,7-trisubstituted octahydro[2]pyrindene as a single diastereoisomer.

引用

页码：7347 / 7357

页数：11

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