青霉属斜卧青霉细胞色素 P450 单加氧酶催化的α-及γ-烯醇的酶促溴环化反应
Enzymatic Bromocyclization of α- and γ-Allenols by Chloroperoxidase from Curvularia inaequalis.
机构信息
Aalto University, Department of Chemistry, Kemistintie 1, 02150, Espoo, Finland.
University of Cologne, Department of Chemistry, Greinstr. 6, 50939, Köln, Germany.
出版信息
ChemistryOpen. 2022 Jan;11(1):e202100236. doi: 10.1002/open.202100236.
Abstract
Vanadate-dependent chloroperoxidase from Curvularia inaequalis catalyzes 5-endo-trig bromocyclizations of α-allenols to produce valuable halofunctionalized furans as versatile synthetic building blocks. In contrast to other haloperoxidases, also the more challenging 5-exo-trig halocyclizations of γ-allenols succeed with this system even though the scope still remains more narrow. Benefitting from the vanadate chloroperoxidase's high resiliency towards oxidative conditions, cyclization-inducing reactive hypohalite species are generated in situ from bromide salts and hydrogen peroxide. Crucial requirements for high conversions are aqueous biphasic emulsions as reaction media, stabilized by either cationic or non-ionic surfactants.
摘要
来自新月弯孢霉的钒依赖型氯过氧化物酶可催化α-烯丙醇的 5-endo-trig 溴环化反应，生成有价值的卤代官能化呋喃，作为多功能的合成砌块。与其他过氧化物酶不同，即使范围仍然更窄，该系统也能成功进行更具挑战性的γ-烯丙醇的 5-exo-trig 卤环化反应。得益于钒氯过氧化物酶对氧化条件的高弹性，溴化物盐和过氧化氢原位生成诱导环化的次卤酸盐反应性物质。高转化率的关键要求是水相两相乳液作为反应介质，由阳离子或非离子表面活性剂稳定。
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