Enzymatic Regioselective Levulinylation of 2′‐Deoxyribonucleosides and 2′‐O‐Methylribonucleosides
Enzymatic Regioselective Levulinylation of 2′‐Deoxyribonucleosides and 2′‐O‐Methylribonucleosides
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2-脱氧核糖核苷和 2-O-甲基核糖核苷的酶促区域选择性乙酰丙酰化
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发表时间：
2005
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通讯作者：
Y. Sanghvi
中科院分区：
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作者：
I. Lavandera;J. García;S. Fernández;M. Ferrero;V. Gotor;Y. Sanghvi
乙酰丙基保护的核苷是固相合成寡核苷酸的关键组成部分。用相应的核苷在有机溶剂中通过酶催化的区域选择性酰化或通过区域选择性酶水解从3 ',5 ' -二- O -乙酰化衍生物合成3 ' -和5 ' - O -乙酰化2 ' -脱氧核糖核苷和2 ' - O -甲基核糖核苷，已经开发出了短而高效的合成方法。脂肪酶介导的各种核苷的去乙酰丙酸乙肟作为酰基供体已经完成。利用固定化的洋葱假单胞菌脂肪酶（PSL‐C）以极好的产量制备了3′‐O‐去乙酰化的2′‐脱氧核糖核苷。同样，南极念珠菌脂肪酶B （CAL‐B）也能高产地提供5′‐O‐去乙酰化核苷。利用CAL - B选择性水解3 ',5 ' -二- O -乙酰丙酸酯制备了3 ' - O -乙酰丙酸2 ' -脱氧核糖核苷和2 ' - O -甲基核糖核苷。
The levulinyl‐protected nucleosides are key building blocks for the solution‐phase synthesis of oligonucleotides. Short and efficient syntheses of 3′‐ and 5′‐O‐levulinylated 2′‐deoxyribonucleosides and 2′‐O‐methylribonucleosides have been developed from the corresponding nucleosides by enzyme‐catalyzed regioselective acylation in organic solvents or from 3′,5′‐di‐O‐levulinyl derivatives by regioselective enzymatic hydrolysis. Lipase‐mediated levulinylation of various nucleosides has been accomplished with acetonoxime levulinate as an acyl donor. Use of immobilized Pseudomonas cepacia lipase (PSL‐C) has furnished 3′‐O‐levulinylated 2′‐deoxyribonucleosides in excellent yields. Similarly, Candida antarctica lipase B (CAL‐B) has provided 5′‐O‐levulinylated nucleosides in high yields. 3′‐O‐Levulinylated 2′‐deoxyribonucleosides and 2′‐O‐methylribonucleosides were prepared via selective hydrolysis of 3′,5′‐di‐O‐levulinate esters using CAL‐B.