140.Retro-metal-ene versus retro-Aldol: mechanistic insight into Rh-catalysed formal [3+2] cycloaddition

Song Liu, Tao Zhang, Lei Zhu, Kangbao Zhong, Jianxian Gong, Zhen Yang*, Ruopeng Bai*, Yu Lan*

Chem. Commun., 2018,54(96), 13551-13554

Theoretical calculations have been performed to investigate the mechanism and stereoselectivity of rhodium-catalysed intramolecular [3+2] cycloaddition for construction of a substituted hexahydropentalene complex. A new C–C bond cleavage mechanism, retro-Aldol-type, is proposed and verified for this Rh-catalysed [3+2] cycloaddition reaction.