对映选择性转移氢化环加成解锁 SF2446 B3 的全合成： Arenimycin 的糖苷配基和 SF2446 型 II 聚酮抗生素。
Enantioselective Transfer Hydrogenative Cycloaddition Unlocks the Total Synthesis of SF2446 B3: An Aglycone of Arenimycin and SF2446 Type II Polyketide Antibiotics.
机构信息
Department of Chemistry, University of Texas at Austin, 105 E 24th Street, Austin, Texas 78712, United States.
出版信息
J Am Chem Soc. 2023 Aug 9;145(31):17461-17467. doi: 10.1021/jacs.3c06225. Epub 2023 Jul 26.
Abstract
The first total synthesis and structure validation of an arenimycin/SF2446 type II polyketide is described, as represented by construction of SF2446 B3, the aglycone shared by this family of type II polyketides. Ruthenium-catalyzed α-ketol-benzocyclobutenone [4 + 2] cycloaddition, which occurs via successive stereoablation-stereoregeneration, affects a double dynamic kinetic asymmetric transformation wherein two racemic starting materials combine to form the congested angucycline bay region with control of regio-, diastereo-, and enantioselectivity. This work represents the first application of transfer hydrogenative cycloaddition and enantioselective intermolecular metal-catalyzed C-C bond activation in target-oriented synthesis.
摘要
本文描述了首例 Arenimycin/SF2446 型 II 聚酮的全合成及结构确证，通过构建 SF2446 B3 （该家族 II 型聚酮的糖苷配基）实现。该反应利用钌催化的 α-酮醇-苯并环丁烯酮 [4 + 2] 环加成反应，通过连续的立体消除-立体再生进行，影响了双动态动力学不对称转化，其中两个外消旋起始物料结合形成拥挤的蒽环霉素海湾区域，控制区域、非对映和对映选择性。这项工作代表了转移氢化加成和对映选择性的分子间金属催化 C-C 键活化在定向合成中的首次应用。
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