As a growing number of chiral bioactive molecules flood the pharmaceutical industry, the importance of efficient enantioselective synthesis and purification of these compounds also increases. Enantioselective organocatalysis has emerged as a powerful synthetic tool complementary to traditional metal-containing catalytic transformations. The catalytic Friedel–Crafts reaction of electron-rich aromatic groups with benzylidenecarbamates has been successfully accomplished using a chiral bisphosphorylimide organocatalyst. The chemical scaffold of bisphosphorylimides is highly structured and ordered, mimicking the active site of an enzyme. The use of triethyl amine as an additive was found to speed up the reaction and prevent product decomposition, resulting in excellent yields (up to 96%) and regioselectivity (only one regioisomer formed). An improved synthesis of the bisphosphorylimide has also been developed using catalytic hydrogenation in a flow reactor. Currently, bisphosphorylimides are underutilized despite their notable potential for catalysis. Full details of catalyst development studies, catalyst loading investigations, substrate scope explorations, and protocol innovations will be presented.

Bisphosphorylimides as organocatalysts for asymmetric Friedel–Crafts reactions

253rd National Meeting (2017)

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