Dedication
Dedicated to Prof. H. Ila on her 80th birthday.
Abstract
Herein, we describe a metal-free facile method for the direct synthesis of α-formamidoalkyl-β-ketodithioesters
by employing easily accessible α-enolic dithioesters (EDTEs) and p-tosylmethyl isocyanide (TosMIC) via base-mediated cross-detosylative C–C coupling
under an open atmosphere. This protocol is mild, operationally simple, highly efficient,
and easy to get highly functionalized products in good-to-high yields. A simple mechanism
involving Cs2CO3 that promotes highly selective nucleophilic attack of the α-carbon of EDTE to TosMIC
followed by hydrolysis is proposed. This efficient approach opens up a new avenue
for exploring the synthesis of multifunctional molecules. The carbonyl, dithioester,
and amide groups of the products offer a platform for late-stage modification, which
could rapidly enrich the structural diversity of the products.
Keywords
Metal-free - α-Enolic dithioesters - TosMIC - Site-selectivity - α-Formamidomethylation
