Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48109-1055, USA.
J Am Chem Soc. 2010 May 12;132(18):6304-5. doi: 10.1021/ja102262v.
A strategy for catalyst-controlled regioselectivity in aldehyde-alkyne reductive couplings has been developed. This strategy is the first where either regiochemical outcome may be selected for a broad range of couplings, without relying on substrate biases or directing effects. The complementary use of small cyclopropenylidene carbene ligands or highly hindered N-heterocyclic carbene ligands allows the regiochemical reversal with unbiased internal alkynes, aromatic internal alkynes, conjugated enynes, or terminal alkynes.
已经开发出一种用于控制醛-炔还原偶联区域选择性的催化剂策略。这是第一个可以在不依赖于底物偏置或导向效应的情况下,为广泛的偶联选择任一区域化学产物的策略。小环丙烯亚基卡宾配体或高度位阻的 N-杂环卡宾配体的互补使用,可以使无偏置内部炔烃、芳基内部炔烃、共轭烯炔或末端炔烃的区域化学反转。