Efficient lipase-catalyzed enantioselective desymmetrization of prochiral 2,2-disubstituted 1,3-propanediols and meso 1,2-diols using 1-ethoxyvinyl 2-furoate.
Efficient lipase-catalyzed enantioselective desymmetrization of prochiral 2,2-disubstituted 1,3-propanediols and meso 1,2-diols using 1-ethoxyvinyl 2-furoate.
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DOI：
10.1002/chin.200226039
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发表时间：
2002-01
期刊：
影响因子：
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通讯作者：
S. Akai;T. Naka;T. Fujita;Y. Takebe;Toshiaki Tsujino;Y. Kita
中科院分区：
文献类型：
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作者：
S. Akai;T. Naka;T. Fujita;Y. Takebe;Toshiaki Tsujino;Y. Kita
利用1-乙氧基乙烯基2-糠酸酯1b开发了一种有效的前手性2，2-二取代1，3-丙二醇的脂肪酶催化的去对称化反应，对于该方法，由于低反应性和容易通过酰基迁移使产物外消旋化，使用乙酸乙烯酯或异丙烯酯的众所周知的方法具有有限的成功。试剂1b具有很高的反应活性，可将各种前手性1，3-二醇转化为具有手性季碳中心的单酯，其ee值为82-99%，这些产物在酸性条件下对外消旋稳定，其呋喃甲酰基与氧化条件相容。反应时间的延长导致单酯的动力学拆分，导致其光学纯度的增加。同样地，内消旋顺式1，2-环烷二醇的去对称化反应不发生外消旋，得到了ee值为82-97%的单酯。
An efficient lipase-catalyzed desymmetrization of prochiral 2,2-disubstituted 1,3-propanediols was developed using 1-ethoxyvinyl 2-furoate 1b, for which the well-known method using vinyl or isopropenyl acetate has had limited success due to low reactivity and easy racemization of the products through acyl group migration. The reagent 1b is highly reactive and converts various prochiral 1,3-diols to the monoesters having a chiral quaternary carbon center with 82-99% ee. These products were stable against racemization under acidic conditions, and their furoyl groups were compatible with oxidative conditions. Prolonging the reaction time led to the kinetic resolution of the monoesters resulting in an increase of their optical purity. The similar desymmetrization of meso cis-1,2-cycloalkanediols gave the monoesters with 82-97% ee without racemization.