吡啶丙氨酸（Pal）-肽催化的对映选择性烯丙酸盐与 N-酰亚胺的加成反应通过一种非典型的“氮杂-Morita-Baylis-Hillman”机制进行。
Pyridylalanine (Pal)-peptide catalyzed enantioselective allenoate additions to N-acyl imines proceed via an atypical "aza-Morita-Baylis-Hillman" mechanism.
机构信息
Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520, United States.
出版信息
Org Lett. 2010 Nov 5;12(21):4800-3. doi: 10.1021/ol101947s.
Mechanistic experiments, including kinetics and hydrogen/deuterium kinetic isotope effects, reveal an "atypical" rate-determining step in a pyridylalanine-peptide catalyzed enantioselective coupling of allenoates and N-acyl imines. Typically, acrylates participate in both the aldehyde-based "Morita-Baylis-Hillman (MBH)" reaction and the imine-based variant (the "aza-MBH") through similar mechanisms, with proton transfer/catalyst regeneration often rate-determining. In contrast, the title reaction exhibits kinetics wherein proton transfer is kinetically silent.
在吡啶丙氨酸肽催化的烯丙酸盐和 N-酰亚胺对映选择性偶联反应中，包括动力学和氢/氘动力学同位素效应在内的机制实验揭示了一个“非典型”的速率决定步骤。通常情况下，丙烯酸盐通过相似的机制参与基于醛的“Morita-Baylis-Hillman (MBH)反应”和基于亚胺的变体（“aza-MBH”），质子转移/催化剂再生通常是速率决定步骤。相比之下，标题反应表现出动力学行为，其中质子转移在动力学上是沉默的。
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