Direct conversion of esters to imines/enamines and applications to polyester waste upcycling†

Abstract

Semi-reductive transformations of esters remain an underdeveloped but valuable class of functional group interconversions. Here, we describe the development of a highly selective method for the interconversion of esters to imines, enamines, aldehydes or amines through an amine-intercepted zirconocene hydride (ZrH)-catalyzed reduction. This protocol employs an inexpensive zirconium catalyst in combination with hydrosilanes and simple unprotected amines. A variety of aryl, benzylic, and aliphatic esters are directly transformed to imines and enamines in up to 99% yield or aldehydes in up to 84% yield, with little-to-no reduction to the corresponding alcohols. The utility of this method for the direct catalytic chemical upcycling of polyester plastic waste is demonstrated through multiple unprecedented depolymerization transformations. Further, the efficient preparation of nitrogen-containing products is also presented, including single-flask multicomponent reactions and the reductive amination of esters.