Generation of Masked TiIIIntermediates from TiIVAmides via β-H Abstraction or Alkyne Deprotonation: An Example of Ti-Catalyzed Nitrene-Coupled Transfer Hydrogenation

Adam J. Pearce; Yukun Cheng; Rachel J. Dunscomb; Ian A. Tonks

doi:10.1021/acs.organomet.0c00577

Generation of Masked Ti^IIIntermediates from Ti^IVAmides via β-H Abstraction or Alkyne Deprotonation: An Example of Ti-Catalyzed Nitrene-Coupled Transfer Hydrogenation

Adam J. Pearce, Yukun Cheng, Rachel J. Dunscomb, Ian A. Tonks

Chemistry (Twin Cities)

Research output: Contribution to journal › Article › peer-review

4 Scopus citations

Abstract

Simple Ti amide complexes are shown to act as sources for masked TiII intermediates via several pathways, as demonstrated through the investigation of a unique Ti-catalyzed nitrene-coupled transfer hydrogenation of 3-hexyne. This reaction proceeds through reduction of azobenzene by a masked TiII catalyst, wherein both amines and 3-hexyne can serve as the hydrogen source/reductant for Ti by forming putative titanaziridines via β-H abstraction or putative titanacyclopentynes via protonolysis, respectively.

Original language	English (US)
Pages (from-to)	3771-3774
Number of pages	4
Journal	Organometallics
Volume	39
Issue number	21
DOIs	https://doi.org/10.1021/acs.organomet.0c00577
State	Published - Nov 9 2020

Bibliographical note

Funding Information:
Financial support was provided by the National Institutes of Health (R35GM119457) and the Alfred P. Sloan Foundation (I.A.T. is a 2017 Sloan Fellow). Instrumentation for the University of Minnesota Chemistry NMR facility was supported from a grant through the National Institutes of Health (S10OD011952).

Publisher Copyright:
© 2020 American Chemical Society.

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title = "Generation of Masked TiIIIntermediates from TiIVAmides via β-H Abstraction or Alkyne Deprotonation: An Example of Ti-Catalyzed Nitrene-Coupled Transfer Hydrogenation",

abstract = "Simple Ti amide complexes are shown to act as sources for masked TiII intermediates via several pathways, as demonstrated through the investigation of a unique Ti-catalyzed nitrene-coupled transfer hydrogenation of 3-hexyne. This reaction proceeds through reduction of azobenzene by a masked TiII catalyst, wherein both amines and 3-hexyne can serve as the hydrogen source/reductant for Ti by forming putative titanaziridines via β-H abstraction or putative titanacyclopentynes via protonolysis, respectively.",

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note = "Funding Information: Financial support was provided by the National Institutes of Health (R35GM119457) and the Alfred P. Sloan Foundation (I.A.T. is a 2017 Sloan Fellow). Instrumentation for the University of Minnesota Chemistry NMR facility was supported from a grant through the National Institutes of Health (S10OD011952). Publisher Copyright: {\textcopyright} 2020 American Chemical Society.",

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AU - Cheng, Yukun

AU - Dunscomb, Rachel J.

AU - Tonks, Ian A.

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