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Formation of Nucleophilic Allylboranes from Molecular Hydrogen and Allenes Catalyzed by a Pyridonate Borane that Displays Frustrated Lewis Pair Reactivity
Author(s) -
Hasenbeck Max,
Ahles Sebastian,
Averdunk Arthur,
Becker Jonathan,
Gellrich Urs
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202011790
Subject(s) - borane , chemistry , hydroboration , frustrated lewis pair , allene , nucleophile , reactivity (psychology) , catalysis , substituent , dissociation (chemistry) , medicinal chemistry , photochemistry , stereochemistry , lewis acids and bases , organic chemistry , medicine , alternative medicine , pathology
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.