Das Siddhartha, Incarvito Christopher D, Crabtree Robert H, Brudvig Gary W
Department of Chemistry, Yale University, 225 Prospect Street, Post Office Box 208107, New Haven, CT 06520-8107, USA.
Science. 2006 Jun 30;312(5782):1941-3. doi: 10.1126/science.1127899.
Although enzymes often incorporate molecular recognition elements to orient substrates selectively, such strategies are rarely achieved by synthetic catalysts. We combined molecular recognition through hydrogen bonding with C-H activation to obtain high-turnover catalytic regioselective functionalization of sp3 C-H bonds remote from the -COOH recognition group. The catalyst contains a Mn(mu-O)2Mn reactive center and a ligand based on Kemp's triacid that directs a -COOH group to anchor the carboxylic acid group of the substrate and thus modify the usual selectivity for oxidation. Control experiments supported the role of hydrogen bonding in orienting the substrate to achieve high selectivity.
尽管酶通常会整合分子识别元件以选择性地定位底物，但合成催化剂很少能实现这种策略。我们将通过氢键的分子识别与C-H活化相结合，以实现远离-COOH识别基团的sp3 C-H键的高周转催化区域选择性官能化。该催化剂包含一个Mn(μ-O)2Mn反应中心和一个基于肯普三酸的配体，该配体引导一个-COOH基团锚定底物的羧酸基团，从而改变通常的氧化选择性。对照实验支持了氢键在定位底物以实现高选择性方面的作用。
