Direct Synthesis of Methylene‐Bridged Bis‐biaryl Carboxylates via Cascade Suzuki Coupling and CH₂Cl₂‐Based Bis‐esterification

Abstract

The multicomponent reactions of iodobenzoic acids, aryl boronic acids, and dichloromethane (DCM) have been designed for the synthesis of various methylene‐bridged bis‐biaryl functionalized carboxylates. Under the catalysis of Pd(OAc)2, the formation of the products involves the cascade Suzuki coupling and CH2Cl2‐base bis‐esterification. The present work offers a direct and practical route to the synthesis of novel carboxylate scaffolds with extended diversity.

Switchable Synthesis of α,α‐Dihalomethyl and α,α,α‐Trihalomethyl Ketones by Metal‐Free Decomposition of Enaminone C=C Double Bond

“…Therefore, considering the easy generation of halogen free radical from many commercial halogen reagents, we envisage that the synthesis of ketones bearing functional αhaloatom such as α,α-dihalomethyl ketones and α,α,αtrihalomethyl ketones can be accessed by scissoring the carbonÀ carbon in the readily available enaminones via free radical pathway. In combination with the usefulness of gem-halogenated compounds [21] as well as the advantage of carbonÀ carbon bond functionalization in organic synthesis, [22] we report herein the unprecedented methods for the tunable synthesis of both α,α-dihalomethyl ketones and α,α,α-trihalomethyl ketones by cleaving the enaminone C=C double bond with free radical transformation under totally metalfree conditions.…”