Amine-Boranes as Transfer Hydrogenation and Hydrogenation Reagents: A Mechanistic Perspective

Samantha Lau, Danila Gasperini, Ruth Webster

Research output: Contribution to journalReview articlepeer-review

88 Citations (SciVal)

Abstract



Transfer hydrogenation (TH) has historically been dominated by Meerwein–Ponndorf–Verley (MPV) reactions. However, with growing interest in amine–boranes, not least ammonia–borane (H3N⋅BH3), as potential hydrogen storage materials, these compounds have also started to emerge as an alternative reagent in TH reactions. In this Review we discuss TH chemistry using H3N⋅BH3 and their analogues (amine–boranes and metal amidoboranes) as sacrificial hydrogen donors. Three distinct pathways were considered: 1) classical TH, 2) nonclassical TH, and 3) hydrogenation. Simple experimental mechanistic probes can be employed to distinguish which pathway is operating and computational analysis can corroborate or discount mechanisms. We find that the pathway in operation can be perturbed by changing the temperature, solvent, amine–borane, or even the substrate used in the system, and subsequently assignment of the mechanism can become nontrivial.
Original languageEnglish
Pages (from-to)14272-14294
Number of pages23
JournalAngewandte Chemie International Edition
Volume60
Issue number26
Early online date25 Feb 2021
DOIs
Publication statusPublished - 21 Jun 2021

Bibliographical note

Funding Information:
. Ruth Webster obtained her undergraduate degree from the University of Strathclyde and her PhD (2011) from the University of Bristol, under the supervision of Prof. Robin Bedford. Following a Commonwealth Postdoctoral Fellowship at the University of British Columbia in the group of Prof. Laurel Schafer, Ruth returned to the UK in 2012, where she is currently an EPSRC Early Career Fellow in Catalysis at the University of Bath

Publisher Copyright:
© 2020 The Authors. Published by Wiley-VCH GmbH

Keywords

  • amine–boranes
  • hydrogenation
  • mechanisms
  • solvolysis
  • transfer hydrogenation

ASJC Scopus subject areas

  • Catalysis
  • General Chemistry

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