Cobalt(I)-mediated preparation of polyborylated cyclohexadienes:: Scope, limitations, and mechanistic insight

被引:61
作者
Geny, Anais
Leboeuf, David
Rouquie, Gabriel
Vollhardt, K. Peter C.
Malacria, Max
Gandon, Vincent
Aubert, Corinne
机构
[1] Univ Paris 06, Chim Organ Lab, F-75252 Paris, France
[2] Univ Calif Berkeley, Dept Chem, Berkeley, CA 94720 USA
[3] Lawrence Berkeley Natl Lab, Div Chem Sci, Berkeley, CA 94720 USA
关键词
boron; cobalt; cross-coupling; density functional calculations; diene ligands;
D O I
10.1002/chem.200700337
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A series of 1,3- and 1,4-diboryl-1,3-cyclohexadienes have been prepared by intermolecular CoCpmediated [2+2+2] cocyclizations of alkynylboronic pinacolate esters with alkenes, followed by oxidative demetallation with iron(III) chloride. The effect of substitution at the borylated alkyne on chemo- and regioselectivities has been studied, suggesting steric control. The proper choice of substituents allowed the preparation of 1,3-diborylated cyclohexadienes in a highly selective manner. Alternatively, 1,4-diborylated cyclohexadienes could be prepared from diborylated diynes. The scope of this reaction has been examined and found to include electron-poor, electron-rich, linear, and cyclic alkenes. The diborylated cyclohexadienes were submitted to single or double Suzuki-Miyaura cross-coupling reactions with haloarenes to afford polyarylated systems. ne mechanism of the title reaction, including the regioselectivity of the cycloaddition steps, has been analyzed by means of DFT computations.
引用
收藏
页码:5408 / 5425
页数:18
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