Synthesis of Functionalized Cycloheptadienones Starting from Phenols and Using a Rhodium/Boron Asymmetric Catalytic System.

Abstract

Skeletal editing offers a unique route to assemble complex architectures from simple feedstocks that are otherwise difficult to obtain. However, the asymmetric version of skeletal editing has not been widely studied. Herein, we present a modular rhodium/boron asymmetric catalytic system that enables ring-expansion of phenols with cyclopropenes to synthesize highly functionalized cycloheptadienones in excellent chemo- and regioselectivities. This unique protocol features with low-catalyst loading, atom and step-economies, and mild neutral reaction conditions. Isotope-labelling experiments and DFT calculations have been conducted to reveal that boron reagent plays a vital role in the whole catalytic cycle.