钯催化的 α-氟代吲哚的对映选择性 α-芳基化反应。
Palladium-Catalyzed, Enantioselective α-Arylation of α-Fluorooxindoles.
机构信息
Department of Chemistry, University of California , Berkeley, California 94720, United States.
出版信息
Org Lett. 2017 Mar 17;19(6):1390-1393. doi: 10.1021/acs.orglett.7b00294. Epub 2017 Mar 6.
Abstract
Transition-metal-catalyzed asymmetric α-arylation of carbonyl compounds is a widely studied method for C-C bond formation. Recently, the α-arylation of α-fluoro ketones has been reported, including enantioselective α-arylation of α-fluoro ketones. However, the asymmetric α-arylation of α-fluoro carbonyl compounds in the carboxylic acid oxidation state has not been reported. We report the enantioselective α-arylation of α-fluorooxindoles with aryl triflates. The reaction occurs in high yield and with high enantioselectivity when catalyzed by a Pd-Segphos complex. This general class of product serves as an enantioenriched, nonenolizable version of α-aryl oxindoles.
摘要
过渡金属催化的羰基化合物不对称 α-芳基化是一种广泛研究的 C-C 键形成方法。最近，已经报道了 α-氟酮的 α-芳基化，包括 α-氟酮的对映选择性 α-芳基化。然而，羧酸氧化态的 α-氟羰基化合物的不对称 α-芳基化尚未报道。我们报告了芳基三氟甲磺酸酯与 α-氟色酮的对映选择性 α-芳基化。当由 Pd-Segphos 配合物催化时，该反应以高产率和高对映选择性发生。这一类通用产物是 α-芳基色酮的对映体富集、非烯醇化的版本。
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2
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