手性铱催化二烯与环氧酮和 N-酰基氮杂环丁酮的对映选择性还原偶联反应，由 2-丙醇介导。
Enantioselective Iridium-Catalyzed Reductive Coupling of Dienes with Oxetanones and N-Acyl-Azetidinones Mediated by 2-Propanol.
机构信息
University of Texas at Austin, Department of Chemistry, 105 E 24th St. (A5300), Austin, TX 78712-1167, USA.
出版信息
Angew Chem Int Ed Engl. 2022 Mar 28;61(14):e202115959. doi: 10.1002/anie.202115959. Epub 2022 Feb 16.
Abstract
Cyclometallated iridium-PhanePhos complexes generated in situ from [Ir(cod)Cl] and (R)-PhanePhos catalyze 2-propanol-mediated reductive couplings of 2-substituted dienes with oxetanone and N-acyl-azetidinones to form branched homoallylic oxetanols and azetidinols with excellent control of regio- and enantioselectivity without C-C cleavage of the strained ring via enantiotopic π-facial selection of transient allyliridium nucleophiles. This work represents the first systematic study of enantioselective additions to symmetric ketones.
摘要
手性环金属铱-PhanePhos 配合物可由 [Ir(cod)Cl] 和 (R)-PhanePhos 原位生成，可催化 2-取代二烯与氧化亚砜和 N-酰基氮杂环丁酮的 2-丙醇介导的还原偶联反应，形成具有优异区域和对映选择性的支化高烯丙基氧化恶唑啉和氮杂环丁醇，而通过瞬态烯丙基铱亲核试剂的对映面选择性 π-面选择性，不会使刚性环发生 C-C 断裂。这项工作代表了对对称酮的对映选择性加成的首次系统研究。
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