α-亚砜酯的酶促拆分与脱羧官能化反应
Enzymatic Resolution and Decarboxylative Functionalization of α-Sulfinyl Esters.
机构信息
Department of Biochemistry, University of Texas Southwestern Medical Center, 75390-9038, Dallas, Texas, USA.
Case Comprehensive Cancer Center, Case Western Reserve University, 44106, Cleveland, Ohio, USA.
出版信息
Chemistry. 2024 Feb 1;30(7):e202302996. doi: 10.1002/chem.202302996. Epub 2023 Dec 11.
Abstract
α-Sulfinyl esters can be readily prepared through thiol substitution of α-bromo esters followed by oxidation to the sulfoxide. Enzymatic resolution with lipoprotein lipase provides both the unreacted esters and corresponding α-sulfinyl carboxylic acids in high yields and enantiomeric ratios. Subsequent decarboxylative halogenation, dihalogenation, trihalogenation and cross-coupling gives rise to functionalized sulfoxides. The method has been applied to the asymmetric synthesis of a potent inhibitor of 15-prostaglandin dehydrogenase.
摘要
α-亚砜酯可以通过α-溴酯的硫醇取代，然后氧化为亚砜来制备。脂蛋白脂肪酶的酶促拆分以高产率和对映体比率提供未反应的酯和相应的α-亚磺酰羧酸。随后的脱羧卤化、二卤化、三卤化和交叉偶联产生官能化的亚砜。该方法已应用于强效 15-前列腺素脱氢酶抑制剂的不对称合成。
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2
The intriguing chemistry and biology of sulfur-containing natural products from marine microorganisms (1987-2020).海洋微生物含硫天然产物的有趣化学与生物学研究（1987 - 2020年）
Mar Life Sci Technol. 2021 May 19;3(4):488-518. doi: 10.1007/s42995-021-00101-2. eCollection 2021 Nov.
3
Iterative synthesis of 1,3-polyboronic esters with high stereocontrol and application to the synthesis of bahamaolide A.具有高立体控制的1,3-聚硼酸酯的迭代合成及其在巴哈马内酯A合成中的应用。
Nat Chem. 2023 Feb;15(2):248-256. doi: 10.1038/s41557-022-01087-9. Epub 2022 Nov 24.
4
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5
Synthesis of Enantiopure Sulfoxides by Concurrent Photocatalytic Oxidation and Biocatalytic Reduction.通过光催化氧化和生物催化还原同时合成对映纯亚砜。
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