对映选择合成
化学
反应性(心理学)
光化学
催化作用
光敏剂
铱
手性路易斯酸
基质(水族馆)
路易斯酸
组合化学
有机化学
替代医学
病理
地质学
海洋学
医学
作者
Benjamin A. Jones,Pearse Solon,Mihai V. Popescu,Ji‐Yuan Du,Robert S. Paton,Martin D. Smith
摘要
Controlling absolute stereochemistry in catalytic photochemical reactions is generally challenging owing to high rates of background reactivity. Successful strategies broadly rely on selective excitation of the reaction substrate when associated with a chiral catalyst. Recent studies have demonstrated that chiral Lewis acid complexes can enable selective energy transfer from a photosensitizer to facilitate enantioselective triplet state reactions. Here, we apply this approach to the enantioselective catalysis of a 6π photocyclization through the design of an iridium photosensitizer optimized to undergo energy transfer to a reaction substrate only in the presence of a chiral Lewis acid complex. Among a group of iridium(III) sensitizers, enantioselectivity and yield closely correlate with photocatalyst triplet energy within a narrow window enabled by a modest reduction in substrate triplet energy upon binding a scandium/ligand complex. These results demonstrate that photocatalyst tuning offers a means to suppress background reactivity and improve enantioselectivity in photochemical reactions.
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