Huddleston Ryan R, Jang Hye-Young, Krische Michael J
Department of Chemistry and Biochemistry, University of Texas at Austin, Austin, Texas 78712, USA.
J Am Chem Soc. 2003 Sep 24;125(38):11488-9. doi: 10.1021/ja030415v.
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.
在1个大气压氢气氛围下，将二炔和乙二醛暴露于阳离子铑（I）催化剂时，会发生区域选择性缩合反应，生成高度不饱和的烯炔产物，且不会过度还原。在手性膦配体存在的情况下，在室温和常压下可获得高对映体过量的还原偶联产物。本研究是催化氢化条件下瞬态生成的有机金属中间体亲电捕获的首批实例之一。
