Cp 2 Ti(II) Mediated Rearrangement of Cyclopropyl Imines.

Autor: Kim J; Department of Chemistry, University of Minnesota-Twin Cities, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States., Egger DT; Department of Chemistry, University of Minnesota-Twin Cities, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States., Frye CW; Department of Chemistry, University of Minnesota-Twin Cities, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States., Beaumier EP; Department of Chemistry, University of Minnesota-Twin Cities, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States., Tonks IA; Department of Chemistry, University of Minnesota-Twin Cities, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States.
Jazyk: angličtina
Zdroj: Organometallics [Organometallics] 2023 Jun 26; Vol. 42 (12), pp. 1331-1338. Date of Electronic Publication: 2023 Mar 15.
DOI: 10.1021/acs.organomet.3c00032
Abstrakt: 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 Cp 2 Ti(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.
Competing Interests: Conflicts of Interest. The authors declare no competing financial interests.
Databáze: MEDLINE
Externí odkaz: