Cp2Ti(II) Mediated Rearrangement of Cyclopropyl Imines

Jaekwan Kim, Dominic T. Egger, Connor W. Frye, Evan P. Beaumier, Ian A. Tonks

Research output: Contribution to journalArticlepeer-review

Abstract

Ti-catalyzed oxidative alkyne carboamination with alkenes and azo compounds can yield either α,β-unsaturated imines or cyclopropyl imines through a common azatitanacyclohexene intermediate. Herein, we report the synthesis of a model azatitanacyclohexene complex (3) through the ring-opening of a cyclopropyl imine with Cp2Ti(BTMSA) (BTMSA = bis(trimethylsilyl)acetylene). 3 readily undergoes thermal or reductant-catalyzed ring contraction to an azatitanacyclopentene (4), analogous to the proposed mechanism for forming α,β-unsaturated imines in the catalytic reaction. A cyclopropyl imine or an α,β-unsaturated imine could be liberated via the oxidation of 3 or 4 with azobenzene, respectively, further implicating the role of these metallacycles in the Ti-catalyzed carboamination reaction.

Original languageEnglish (US)
Pages (from-to)1331-1338
Number of pages8
JournalOrganometallics
Volume42
Issue number12
DOIs
StatePublished - Jun 26 2023

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Publisher Copyright:
© 2023 American Chemical Society.

PubMed: MeSH publication types

  • Journal Article

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