Ferrocenium Boronic Acid Catalyzed Deoxygenative Coupling of Alcohols with Carbon- and Nitrogen-Based Borate and Silane Nucleophiles
作者:Jake J. Blackner、Deirdre M. Rooney、Joshua W. Hollett、J. Adam McCubbin
DOI:10.1021/acs.joc.3c00463
日期:2023.7.7
yields, increased diversity of the alcohol substrate scope, and high E/Z selectivity. Furthermore, the reaction proceeds under mild conditions and yields up to 98%. Computational studies provide a rationalization for a mechanistic pathway for the retention of E/Z stereochemistry when E or Z alkenyl silanes are used as nucleophiles. This methodology is complementary to existing methodologies for deoxygenative
开发了硼酸催化的碳-碳和碳-氮键形成反应,用于各种π-活化醇的官能化。二茂铁硼酸六氟锑酸盐被认为是醇与各种三氟硼酸钾和有机硅烷亲核试剂直接脱氧偶联的有效催化剂。比较这两类亲核试剂,使用有机硅烷可提高反应产率、增加醇底物范围的多样性以及高E / Z选择性。此外,该反应在温和条件下进行,收率高达98%。计算研究为当E或Z烯基硅烷用作亲核试剂时保留E / Z立体化学的机制途径提供了合理化。该方法是对涉及有机硅烷的脱氧偶联反应的现有方法的补充,并且它对各种有机硅烷亲核体子类型有效,包括烯丙基、乙烯基和炔丙基三甲基硅烷。