Room temperature ring-opening metathesis of pyridines by a transient TiC linkage

被引:75
作者
Bailey, Brad C.
Fan, Hongjun
Huffman, John C.
Baik, Mu-Hyun [1 ]
Mindiola, Daniel J.
机构
[1] Indiana Univ, Ctr Mol Struct, Dept Chem, Bloomington, IN 47405 USA
[2] Indiana Univ, Sch Informat, Bloomington, IN 47405 USA
关键词
D O I
10.1021/ja061590p
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The transient titanium alkylidyne complex (PNP)Ti≡CtBu (PNP = N[2-P(CHMe2)2-4-methylphenyl]2-), prepared from α-hydrogen abstraction of the corresponding alkylidene-alkyl species (PNP)Ti=CHtBu(CH2tBu), can readily cleave the C - N bond of N-heterocycles such as pyridine and 4-picoline at room temperature to afford azametallabicyclic systems. Experimental and theoretical studies strongly favor a ring-opening metathesis pathway where [2 + 2] cycloaddition of pyridine across the Ti≡C linkage ultimately leads to C - N bond rupture. Copyright © 2006 American Chemical Society.
引用
收藏
页码:6798 / 6799
页数:2
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