Organic Solvent-Tolerant Marine Microorganisms as Catalysts for Kinetic Resolution of Cyclic β-Hydroxy Ketones
Organic Solvent-Tolerant Marine Microorganisms as Catalysts for Kinetic Resolution of Cyclic β-Hydroxy Ketones
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DOI：
10.1007/s10126-017-9755-7
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发表时间：
2017-08-01
影响因子：
3
通讯作者：
Liu, Lan
中科院分区：
文献类型：
--
作者：
Chen, Bi-Shuang;Liu, Hui;Liu, Lan
手性环状β-羟基酮代表了生产具有生物学意义的天然产物的关键基序。虽然分子结构简单，但它们需要繁琐的合成步骤才能获得它们，并且它们的合成仍然是有机化学中的一个挑战。在这篇报道中，我们描述了一种简单的方法，对映体富集的（R）-和（S）-3-羟基环戊酮2a，（R）-和（S）-3-羟基环己酮2b，（R）-和（S）-3-羟基环庚酮2c涉及使用海洋微生物的全细胞作为催化剂和乙酸乙烯酯的酰基供体和溶剂的外消旋体的酯交换拆分。从海洋沉积物的广泛收集的菌株进行了筛选，并发现7株显着催化的决议在一个不对称的方式。使用沙雷氏菌属菌株，（R）-2a以27%产率和92%ee分离，（S）-2a以65%产率和43%ee分离，对应于37的E值;（R）-2b以25%产率和91%ee分离，（S）-2b以67%产率和39%ee分离，对应于40的E值;（R）-2c以30%产率和96%ee分离，（S）-2c以63%产率和63%ee分离，对应于75的E值。
Chiral cyclic beta-hydroxy ketones represent key motifs in the production of natural products of biological interest. Although the molecules are structurally simple, they require cumbersome synthetic steps to get access to them and their synthesis remains a challenge in organic chemistry. In this report, we describe a straightforward approach to enantiomerically enriched (R)- and (S)-3-hydroxycyclopentanone 2a, (R) - and (S)-3-hydroxycyclohexanone 2b, and (R) -and (S)-3-hydroxycycloheptanone 2c involving a transesterification resolution of the racemates using whole cells of marine microorganisms as catalysts and vinyl acetate the acyl donor and solvent. Twenty-six strains from a wide collection of isolates from marine sediments were screened, and seven strains were found to markedly catalyze the resolution in an asymmetric fashion. Using the strain Serratia sp., (R)-2a was isolated in 27% yield with 92% ee and (S)-2a in 65% yield with 43% ee, corresponding to an E-value of 37; (R)-2b was isolated in 25% yield with 91% ee and (S)-2b in 67% yield with 39% ee, corresponding to an E-value of 40; and (R)-2c was isolated in 30% yield with 96% ee and (S)-2c in 63% yield with 63% ee, corresponding to an E-value of 75.