UV induced hydrophosphination of dimethyl 2-vinylcyclopropane-1,1-dicarboxylate towards phosphine chalcogenides

Dimethyl 2-vinylcyclopropane-1,1-dicarboxylate underwent a hydrophosphination reaction with either a primary or secondary phosphine under photolytic conditions. Notably, a free radical initiator was not required. The resulting tertiary phosphines were derivatized using S-8 to afford moisture and air stable yellow or colorless oils in a 27%-73% isolated yield. A series of control reactions were performed, and we propose that this UV induced hydrophosphination reaction proceeds through a radical mechanism.

Automated summary

Dimethyl 2-vinylcyclopropane-1,1-dicarboxylate can undergo hydrophosphination reaction with primary or secondary phosphine without the need for a free radical initiator, under photolytic conditions. The resulting tertiary phosphines, after derivatization with S-8, can be obtained in a 27%-73% yield as moisture and air stable yellow or colorless oils. Control reactions suggest that this UV-induced hydrophosphination reaction proceeds through a radical mechanism.