DIASTEREOSELECTIVE AND ENANTIOSELECTIVE SYNTHESIS OF 1,2-TRANS-SUBSTITUTED CYCLOALKANECARBOXYLATES AND SULFONES BY MICHAEL-INITIATED CYCLIZATION VIA SAMP RAMP HYDRAZONES

被引：19
作者：
ENDERS, D
SCHERER, HJ
RUNSINK, J
机构：
[1] Institut für Organische Chemie, Technischen Hochschule Aachen, Aachen, D-52074
来源：
CHEMISCHE BERICHTE-RECUEIL | 1993年 / 126卷 / 08期
关键词：
SAMP HYDRAZONES; RAMP HYDRAZONES; MIRC REACTIONS; CYCLOALKANECARBOXYL ACID ESTERS; SULFONES;
D O I：
10.1002/cber.19931260825
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
An efficient and flexible synthesis of 1,2-trans-substituted cycloalkanecarboxylates and sulfones of high diastereo- and enantiomeric purity is described. The key step of the procedure is a Michael-initiated ring closure (MIRC) reaction employing the SAMP/RAMP hydrazone method. Depending on the chain length of the omega-bromo(iodo)enoates 2, 3 and the type of ketone SAMP-hydrazone 1, 3-, 5-, 6- and 7-membered cycloalkane-carboxylates 4-7 or cyclopentanesulfones 24 bearing two or three stereogenic centers are formed with very high asymmetric induction. In the same manner, MIRC reactions with omega-(ethoxycarbonyl)enoate 26 give rise to 3-substituted cyclopentanone-2-carboxylates 27, but with lower overall chemical yields. The relative and absolute configurations are based on X-ray structure analyses, spectroscopic and mechanistic investigations.
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页码：1929 / 1944
页数：16
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