通过晶体固体中构型捕获自由基对的组合实现邻位立体化学叔中心和季中心的对映体特异性合成。

Enantiospecific synthesis of vicinal stereogenic tertiary and quaternary centers by combination of configurationally-trapped radical pairs in crystalline solids.

作者信息

Ellison Martha E, Ng Danny, Dang Hung, Garcia-Garibay Miguel A

机构信息

Department of Chemistry and Biochemistry, University of California-Los Angeles, Los Angeles, California 90095-1569, USA.

出版信息

Org Lett. 2003 Jul 10;5(14):2531-4. doi: 10.1021/ol0347803.

DOI:10.1021/ol0347803

PMID:12841773

Abstract

[reaction: see text] Photochemical irradiation of crystalline (2R,4S)-2-carbomethoxy-4-cyano-2,4-diphenyl-3-butanone 1 led to highly efficient decarbonylation reactions. Experiments with optically pure and racemic crystals showed that the intermediate radical pairs undergo a highly diastereo- and enantiospecific radical-radical combination that leads to the formation of two adjacent stereogenic centers in good chemical yield and with high chemical control. Reactions with chiral crystals occurred with quantitative enantiomeric yields and >95% diastereomeric yields.

摘要

[反应：见正文] 对晶体（2R,4S）-2-甲氧羰基-4-氰基-2,4-二苯基-3-丁酮1进行光化学辐照会引发高效的脱羰反应。对光学纯晶体和外消旋晶体进行的实验表明，中间体自由基对会发生高度非对映和对映特异性的自由基-自由基结合，从而以良好的化学产率和高度的化学控制形成两个相邻的手性中心。与手性晶体的反应以定量的对映体产率和>95%的非对映体产率发生。