化学
环加成
区域选择性
环丙烯
甲亚胺叶立德
1,3-偶极环加成
叶立德
药物化学
环丙烷
计算化学
组合化学
光化学
有机化学
戒指(化学)
催化作用
作者
Alexander S. Filatov,Siqi Wang,Olesya V. Khoroshilova,Stanislav V. Lozovskiy,Anna G. Larina,Vitali M. Boitsov,А. V. Stepakov
标识
DOI:10.1021/acs.joc.9b00753
摘要
A stereo- and regioselective 1,3-dipolar cycloaddition of the stable ninhydrin-derived azomethine ylide [2-(3,4-dihydro-2 H-pyrrolium-1-yl)-1-oxo-1 H-inden-3-olate, DHPO] to differently substituted cyclopropenes has been established. As a result, an efficient synthetic protocol was developed for the preparation of biologically relevant spiro[cyclopropa[ a]pyrrolizine-2,2'-indene] derivatives. DHPO has proved to be an effective trap for such highly reactive and unstable substrates as parent cyclopropene, 1-methylcyclopropene, 1-phenylcyclopropene, and 1-halo-2-phenylcyclopropenes. It has also been found that 3-nitro-1,2-diphenylcyclopropene undergoes a nucleophilic substitution reaction in alcohols and thiols to afford 3-alkoxy- and 3-arylthio-substituted 1,2-diphenylcyclopropenes, which can be captured as corresponding 1,3-dipolar cycloadducts in the presence of DHPO. These new approaches provide a straightforward strategy for the synthesis of functionally substituted cyclopropa[ a]pyrrolizine derivatives. The factors governing regio- and stereoselectivity have been revealed by means of quantum mechanical calculations (M11 density functional theory), including previously unreported Nylide- Hcyclopropene second-orbital interactions. The outcome of this work contributes to the study of 1,3-dipolar cycloaddition, as well as enriches chemistry of cyclopropenes and methods for the construction of polycyclic compounds with cyclopropane fragments.
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