Cp2Ti(II) Mediated Rearrangement of Cyclopropyl Imines

被引：2
作者：
Kim, Jaekwan [1 ]
Egger, Dominic T. [1 ]
Frye, Connor W. [1 ]
Beaumier, Evan P. [1 ]
Tonks, Ian A. [1 ]
机构：
[1] Univ Minnesota Twin Cities, Dept Chem, Minneapolis, MN 55455 USA
来源：
ORGANOMETALLICS | 2023年 / 42卷 / 12期
基金：
美国国家卫生研究院;
关键词：
C-H BOND; ELECTRON-TRANSFER; COMPLEXES; CATALYSIS; ALKYNES; CARBOAMINATION; TITANOCENE; NITRILES; AMINES;
D O I：
10.1021/acs.organomet.3c00032
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
Ti-catalyzed oxidative alkyne carboamination with alkenes and azo compounds can yield either alpha,beta-unsaturated imines or cyclopropyl imines through a common azatitanacyclo-hexene 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 reduc-tant-catalyzed ring contraction to an azatitanacyclopentene (4), analogous to the proposed mechanism for forming alpha,beta-unsaturated imines in the catalytic reaction. A cyclopropyl imine or an alpha,beta-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.
引用
收藏
页码：1331 / 1338
页数：8
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