Preparation of C2-symmetric bicyclo[2.2.2]octa-2,5-diene ligands and their use for rhodium-catalyzed asymmetric 1,4-addition of arylboronic acids
Preparation of C2-symmetric bicyclo[2.2.2]octa-2,5-diene ligands and their use for rhodium-catalyzed asymmetric 1,4-addition of arylboronic acids
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DOI：
10.1021/jo047831y
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发表时间：
2005-04-01
影响因子：
3.6
通讯作者：
Hayashi, T
中科院分区：
文献类型：
--
作者：
Otomaru, Y;Okamoto, K;Hayashi, T
以双环[2.2.2]辛烷-2，5-二酮为关键中间体，合成了对映体纯的C2-对称双环[2.2.2]辛烷-2，5-二烯，其2位和5位分别含有苄基、苯基和取代苯基。这些手性二烯配体被成功地应用于铑催化的芳基硼酸与α，β-不饱和酮的不对称1，4-加成反应。高的对映选择性（高达99%ee），以及高催化活性，观察到除了环状和线性基板。
C-2-Syinmetric bicyclo [2.2.2]octa-2,5-dienes containing benzyl, phenyl, and substituted phenyl groups at 2 and 5 positions were prepared enantiomerically pure by way of bicyclo[2.2.2]octane-2,5-dione as a key intermediate. These chiral diene ligands were successfully applied to rhodium-catalyzed asymmetric 1,4-addition of arylboronic acids to alpha,beta-unsaturated ketones. High enantioselectivity (up to 99% ee) as well as high catalytic activity was observed in the addition to both cyclic and linear substrates.