Multicomponent reactions of phosphines, enynedioates and benzylidene malononitriles generated highly substituted cyclopentenes through an unexpected phosphine alpha-addition-delta-evolvement of an anion pathway

作者：Chuang Shih Ching^*; Sung Shih Ping; Deng Jie Cheng; Chiou Mong Feng; Hsu Day Shin

来源：Organic and Biomolecular Chemistry, 2016, 14(7): 2306-2317.

DOI：10.1039/c5ob02445e

Multicomponent reactions of phosphines, enynedioates and benzylidene malononitriles provide highly substituted syn-selective cyclopentenes appending the phosphorus ylide moiety in good yield with a diastereoselectivity of up to 100% through resonance-derived 1,5-dipolar species as the key intermediates, via the nucleophilic alpha(delta')-attack of phosphines toward enynedioates followed by addition to benzylidene malononitriles and 5-exo-dig cyclization. Through computational analyses, the overall reactions for the formation of syn- and anti-diastereomers are both exothermic with 65.6 and 66.3 kcal mol(-1) at the B3LYP-D3/6-31G(d) level of theory and were found to be kinetically controlled, which favours the formation of syn-diastereomers.

• 出版日期2016