New bioorganic reagents: Evolved cyclohexanone monooxygenases - Why is it more selective?
New bioorganic reagents: Evolved cyclohexanone monooxygenases - Why is it more selective?
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DOI：
10.1021/jo061349t
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发表时间：
2006-10-27
影响因子：
3.6
通讯作者：
Clouthier, Christopher M.
中科院分区：
文献类型：
--
作者：
Kayser, Margaret M.;Clouthier, Christopher M.
以4-羟基环己酮的Baeyer-Villiger氧化反应为催化剂，研究了环己酮单加氧酶（CHMO）的4个突变体对4-取代和4，4-二取代环己酮的催化作用。几个优秀的催化匹配（突变体/底物）进行了鉴定。然而，最重要的是发现，在许多情况下，具有单一交换的突变体Phe 432 Ser被证明作为催化剂比野生型CHMO更稳健和更具选择性。所有生物转化均在实验室规模上进行，从而能够对产品进行全面表征。建立了两种产物的绝对构型。提出了一个模型，建议在对映体选择性控制的432丝氨酸残基的可能作用。
Four mutants of the cyclohexanone monooxygenase (CHMO) evolved as catalysts for Baeyer-Villiger oxidation of 4-hydroxycyclohexanone were investigated as catalysts for a variety of 4-substituted and 4,4-disubstituted cyclohexanones. Several excellent catalytic matches (mutant/substrate) were identified. The most important, however, is the finding that, in a number of cases, a mutant with a single exchange, Phe432Ser, was shown to be as robust and more selective as a catalyst than the wild-type CHMO. All biotransformations were performed on a laboratory scale, allowing full characterization of the products. The absolute configurations of two products were established. A model suggesting a possible role of the 432 serine residue in enantioselectivity control is proposed.