Mechanistic investigation leads to a synthetic improvement in the hydrolytic kinetic resolution of terminal epoxides
Mechanistic investigation leads to a synthetic improvement in the hydrolytic kinetic resolution of terminal epoxides
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DOI：
10.1021/ja038590z
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发表时间：
2004-02-11
影响因子：
15
通讯作者：
Jacobsen, EN
中科院分区：
文献类型：
--
作者：
Nielsen, LPC;Stevenson, CP;Jacobsen, EN
用反应热法进行动力学分析，研究了末端环氧化物的水解动力学拆分机理。手性(Salen)Co−X络合物(X=OAc，OTS，Cl)在反应过程中发生不可逆转化为(Salen)Co−OH，在双金属协同催化机理中既是前催化剂又是助催化剂.这一洞察导致了对合成有用的末端环氧化物的HKR更具活性的催化剂的鉴定。
The mechanism of the hydrolytic kinetic resolution (HKR) of terminal epoxides was investigated by kinetic analysis using reaction calorimetry. The chiral (salen)Co−X complex (X = OAc, OTs, Cl) undergoes irreversible conversion to (salen)Co−OH during the course of the HKR and thus serves as both precatalyst and cocatalyst in a cooperative bimetallic catalytic mechanism. This insight led to the identification of more active catalysts for the HKR of synthetically useful terminal epoxides.