Hidden Boron Catalysis: A Cautionary Tale on TMEDA Inhibition

Org Lett. 2024 Nov 8;26(44):9564-9567. doi: 10.1021/acs.orglett.4c03591. Epub 2024 Oct 28.

Abstract

Hidden boron catalysis plagues catalyzed hydroboration reactions, with the "catalyst" acting to mediate the decomposition of HBpin/HBcat to BH3 which is the actual (hidden) catalyst. N,N,N',N'-Tetramethylethylenediamine (TMEDA) has been used to identify hidden boron catalysis through trapping/inhibition. Kinetic analyses showed that TMEDA inhibition is only applicable below 60 °C and that other amine traps are likewise ineffective. Awareness of this temperature limitation reveals widespread hidden catalysis in previous methods and should limit future false negative tests.