Highly selective synthesis of all-carbon tetrasubstituted alkenes by deoxygenative alkenylation of carboxylic acids

Abstract

AbstractThe synthesis of all-carbon tetrasubstituted olefins under mild reaction conditions is challenging because of the inevitable issues including significant steric hindrance and the uncontrolled Z/E stereoselectivity. In this paper, we report the synthesis of all-carbon tetrasubstituted alkenes from readily available carboxylic acids and alkenyl triflates with the synergistic catalysis of cyclo-octa-1,5-diene(tetramethyl-1,4-benzoquinone)nickel and visible light under an air atmosphere, thus avoiding the need for a glovebox or a Schlenk line. A wide range of aromatic carboxylic acids and cyclic and acyclic alkenyl triflates undergo the C-C coupling process smoothly, forming structurally diverse alkenes stereospecifically in moderate to good yields. The practicality of the method is further illustrated by the late-stage modification of complex molecules, the one pot synthesis and gram-scale applications. This is an important step towards the valuable utilization of carboxylic acids, and it also simplifies the experimental operation of metallophotoredox catalysis with moisture sensitive nickel(0) catalysis.