Formation of Nucleophilic Allylboranes from Molecular Hydrogen and Allenes Catalyzed by a Pyridonate Borane that Displays Frustrated Lewis Pair Reactivity.

Formation of Nucleophilic Allylboranes from Molecular Hydrogen and Allenes Catalyzed by a Pyridonate Borane that Displays Frustrated Lewis Pair Reactivity.
Angew Chem Int Ed Engl. 2020 Sep 14;:
Authors: Gellrich U, Hasenbeck M, Ahles S, Averdunk A, Becker J
Abstract
Here we report the in situ generation of nucleophilic allylboranes from H 2 and allenes mediated by a pyridonate borane that displays frustrated Lewis Pair reactivity. Experimental and computational mechanistic investigations reveal that upon H 2 activation, the covalently bound pyridonate substituent becomes a datively bound pyridone ligand. Dissociation of the formed pyridone borane complex liberates Piers borane and enables a hydroboration of the allene. The allylboranes generated in this way are reactive towards nitriles. A catalytic protocol for the formation of allylboranes from H 2 and allenes and the allylation of nitriles has been devised. This catalytic reaction is a conceptually new way to use molecular H 2 in organic synthesis.
PMID: 32926511 [PubMed - as supplied by publisher]

Source: Angewandte Chemie - September 13, 2020 Category: Chemistry Authors: Gellrich U, Hasenbeck M, Ahles S, Averdunk A, Becker J Tags: Angew Chem Int Ed Engl Source Type: research