First catalytic reductive coupling of 1,3-diynes to carbonyl partners: A new regio- and enantioselective C-C bond forming hydrogenation
First catalytic reductive coupling of 1,3-diynes to carbonyl partners: A new regio- and enantioselective C-C bond forming hydrogenation
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DOI：
10.1021/ja030415v
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发表时间：
2003-09-24
影响因子：
15
通讯作者：
Krische, MJ
中科院分区：
文献类型：
--
作者：
Huddleston, RR;Jang, HY;Krische, MJ
当二炔和乙二醛在1个大气压的氢气下暴露于阳离子Rh（I）催化剂时，发生区域选择性缩合，得到高度不饱和的烯炔产物，而没有过度还原。在手性膦配体的存在下，在环境温度和压力下以高对映体过量获得还原偶联产物。本研究是在催化氢化条件下瞬时获得的有机金属中间体的亲电捕获的第一个例子。
Upon exposure of diynes and glyoxals to cationic Rh(I) catalysts under 1 atm of hydrogen gas, regioselective condensation occurs to afford highly unsaturated enyne products without over-reduction. In the presence of chiral phosphine ligands, reductive coupling products are obtained in high enantiomeric excess at ambient temperature and pressure. The present studies are among the first examples of the electrophilic trapping of organometallic intermediates obtained transiently under the conditions of catalytic hydrogenation.