LIPASE-CATALYZED IRREVERSIBLE TRANSESTERIFICATIONS USING ENOL ESTERS AS ACYLATING REAGENTS - PREPARATIVE ENANTIOSELECTIVE AND REGIOSELECTIVE SYNTHESES OF ALCOHOLS, GLYCEROL DERIVATIVES, SUGARS, AND ORGANOMETALLICS
LIPASE-CATALYZED IRREVERSIBLE TRANSESTERIFICATIONS USING ENOL ESTERS AS ACYLATING REAGENTS - PREPARATIVE ENANTIOSELECTIVE AND REGIOSELECTIVE SYNTHESES OF ALCOHOLS, GLYCEROL DERIVATIVES, SUGARS, AND ORGANOMETALLICS
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DOI：
10.1021/ja00229a041
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发表时间：
1988-10-12
影响因子：
15
通讯作者：
WONG, CH
中科院分区：
文献类型：
--
作者：
WANG, YF;LALONDE, JJ;WONG, CH
异丙烯和乙烯基酯已被发现用于脂肪酶催化的许多羟基化合物的立体选择性酰化反应，包括甘油和丝氨醇衍生物、二茂铁乙醇、糖和其他醇。与使用烷基酯作为酰化试剂的其他酯交换反应相比，该反应速度更快、选择性更高、更容易优化。从酯交换反应中释放出来的酒精迅速互变为挥发性乙醛或丙酮，使该过程不可逆，产品分离更简单。该方法特别适用于某些手性化合物的合成，如二茂铁乙酯和酰基糖，这些化合物在水溶液中很难制备。与水解法相比，以正构烷基酯为酰化试剂的酯交换反应慢约102-104倍，以烯醇酯为酰化试剂的酯交换反应慢约10倍。在某些情况下，酯交换反应的选择性不如水解物。
Isopropenyl and vinyl esters have been found to be useful for lipase-catalyzed stereoselective acylation of a number of hydroxy compounds including glycerol and serinol derivatives, ferrocenylethanol, sugars, and other alcohols. The reactions are faster, more selective, and easier to optimize than other transesterifications using alkyl esters as acylating reagents. The alcohol freed from the transesterification rapidly tautomerizes to volatile acetaldehyde or acetone, making the process irreversible and simpler for product isolation. The process is particularly useful for synthesis of certain chiral compounds, such as ferrocenyl ethyl esters and acyl sugars, which are difficult to prepare in aqueous solution. Compared to hydrolysis, transesterifications are about 102-104 times slower with normal alkyl esters as acylating reagents and about 10 times slower with the enol esters as acylating reagents. In some cases, transesterifications are less selective than hydrolyses.