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Generation of Masked Ti^II Intermediates from Ti^IV Amides 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 Ti^II 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 Ti^II 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.

SUBMITTER: Pearce AJ

PROVIDER: S-EPMC8315702 | biostudies-literature | 2020 Nov

REPOSITORIES: biostudies-literature

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Generation of Masked TiII Intermediates from TiIV Amides via β-H Abstraction or Alkyne Deprotonation: An Example of Ti-Catalyzed Nitrene-Coupled Transfer Hydrogenation.

Pearce Adam J AJ Cheng Yukun Y Dunscomb Rachel J RJ Tonks Ian A IA

Organometallics 20201020 21

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 titanacyclope ...[more]

PMID: 34321708

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