手性二苯并恶嗪盐叶立德与炔烃和富勒烯 C60 的立体选择性环加成反应。3-芳基二苯并[b,f]吡咯并[1,2-d][1,4]恶嗪体系的构象行为。

Stereoselective cycloaddition of dibenzoxazepinium ylides to acetylenes and fullerene C60. Conformational behavior of 3-aryldibenzo[b,f]pyrrolo[1,2-d][1,4]oxazepine systems.

机构信息

Department of Chemistry, Saint Petersburg State University, Universitetskii pr. 26, 198504 St. Petersburg, Russia.

出版信息

J Org Chem. 2010 Aug 6;75(15):5211-5. doi: 10.1021/jo100966j.

PMID:20604511

Abstract

Cycloaddition of dibenzoxazepinium ylides to acetylene carboxylates leads to cis-3-aryl-3,13b-dihydrodibenzo[b,f]pyrrolo[1,2-d][1,4]oxazepinecarboxylates, which smoothly dehydrogenate to the corresponding pyrrole derivatives. The o-bromophenyl-substituted pyrrole, in contrast to the pyrroline analogue, demonstrates atropoisomerism. Stereoselective cycloaddition of dibenzoxazepinium ylides to fullerene C(60) gives rise to fulleropyrrolidines with cis-configuration. Restricted Ph group rotation is found in the phenyl derivative. Only one of two possible atropoisomers is formed in the reaction of o-bromophenyl-substituted ylide with fullerene C(60). Details of cycloaddition and conformational behavior of cycloadducts were studied by DFT computations.

摘要

二苯并恶嗪鎓叶立德与乙炔羧酸酯的环加成反应生成顺式-3-芳基-3,13b-二氢二苯并[b,f]吡咯[1,2-d][1,4]恶嗪并[1,2-c]吡啶-3,13-二羧酸酯，后者可顺利脱氢生成相应的吡咯衍生物。与吡咯啉类似物相比，邻溴苯基取代的吡咯表现出阻转异构现象。二苯并恶嗪鎓叶立德与富勒烯 C(60)的立体选择性环加成反应生成具有顺式构型的富勒烯吡咯里定。在苯基衍生物中发现 Ph 基团旋转受到限制。邻溴苯基取代的叶立德与富勒烯 C(60)反应时，仅形成两种可能的阻转异构体之一。通过 DFT 计算研究了环加成和环加成产物的构象行为的详细信息。