Biocatalytic desulfurization of arylsulfonates.
Biocatalytic desulfurization of arylsulfonates.
复制标题
芳基磺酸盐的生物催化脱硫。
DOI：
10.1016/0968-0896(94)85018-6
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发表时间：
1994
影响因子：
3.5
通讯作者：
J. W. Frost
中科院分区：
文献类型：
--
作者：
M. Dudley;J. W. Frost
已分离出一种微生物菌株Klebsiella oxytocaKS3D，其能够在生长期间利用芳基磺酸盐作为硫的唯一来源。以intactK. oxytocaKS3D导致芳基磺酸盐转化为相应的酚。甚至携带取代基的芳基磺酸盐，显着改变空间和电子特性的底物。从取代的芳基磺酸酯仅产生单一的区域异构体。根据生物催化脱硫的产物和同位素氧在富氧条件下脱硫时酚类产物中的掺入，可以排除水解机理。两种反应类型，这可能会模仿发生在微生物脱硫的芳基磺酸盐的化学进行了检查。第一个反应涉及通过单电子还原将适当取代的芳基磺酸盐转化为苯酚，然后通过自由基阴离子与分子氧的反应。使用芳基磺酸盐和芳基砜与烷氧基自由基的分子内反应的第二反应未能实现脱硫。除了机理评价外，还对K. oxytocaKS3D是从它的相关性的角度来检查煤的有机硫组分的脱硫和其可能用于工业制造酚。
A microbial strain,Klebsiella oxytocaKS3D, has been isolated which is capable of exploiting arylsulfonates as a sole source of sulfur during growth. The desulfurization catalyzed by intactK. oxytocaKS3D results in the conversion of arylsulfonates into the corresponding phenols. Even arylsulfonates carrying substituents which significantly alter steric and electronic characteristics are substrates. Only a single regioisomer is produced from substituted arylsulfonates. Based on the products formed from the biocatalytic desulfurizations and incorporation of isotopic oxygen in phenolic product when the desulfurization is run under18O-enriched oxygen, hydrolysis mechanisms can be eliminated from consideration. Two reaction types which might mimic the chemistry occurring during microbial desulfurization of arylsulfonates were examined. The first reaction involved conversion of appropriately substituted arylsulfonates into phenols by single electron reduction followed by reaction of the radical anions with molecular oxygen. A second reaction using intramolecular reaction of arylsulfonates and arylsulfones with alkoxy radicals failed to achieve desulfurization. In addition to mechanistic evaluation, desulfurization of arylsulfonates catalyzed byK. oxytocaKS3D is examined from the perspective of its relevance to desulfurization of the organosulfur components of coal and its possible use for industrial manufacture of phenols.