Process Development of Heterogeneous Rh Catalyzed Carbene Transfer Reactions Under Continuous Flow Conditions.

Abstract

A very simple Rh-based catalyst operates under heterogeneous flow conditions for the carbene transfer of methyl diazoacetate (MDA) with several substrates. Two different methods for heterogenizing the catalyst in a column reactor have been applied. Different X-H (X=O, S, Si, CH2 ) were successfully functionalized by the carbene and cyclopropenation was performed under very mild continuous flow conditions. Following these promising results, catalyst recycling experiments using both methodologies were conducted in which up to 5 catalytic cycles have been achieved for the carbene O-H insertion reaction and interestingly, a sequential transformation of different substrates with up to 10 consecutive runs per reactor were achieved with no loss in the catalytic activity, thus allowing the production of families of compounds.