Cooperative Stereoinduction in Asymmetric Photocatalysis.
Cooperative Stereoinduction in Asymmetric Photocatalysis.
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DOI：
10.1021/jacs.2c00063
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发表时间：
2022-03-09
影响因子：
15
通讯作者：
Yoon, Tehshik P.
中科院分区：
文献类型：
--
作者：
Chapman, Steven J.;Swords, Wesley B.;Le, Christine M.;Guzei, Ilia A.;Toste, F. Dean;Yoon, Tehshik P.
复杂有机反应中的立体诱导通常涉及多种立体控制元件的影响。这些之间的相互作用通常可以导致观察到显着的协同效应，这些效应在匹配和不匹配的立体分化手性元素组之间提供不同的速率和选择性。阐明基态化学反应中的匹配/不匹配效应是现代立体控制合成成熟过程中至关重要的主题。然而，用于控制光化学反应的稳健方法的开发是一个相对较新的发展，并且激发态对映选择性光反应中类似的协同立体控制效应之前尚未被记录。在此，我们描述了用于乙烯基吡啶的高度对映选择性[2+2]光环加成的串联手性光催化剂/布朗斯台德酸策略。重要的是，匹配和不匹配的手性催化剂对在一系列偶联伙伴中表现出不同的反应速率和对映选择性。我们没有观察到光催化剂之间基态相互作用的证据，并得出结论，这些效应是由它们在瞬态激发态组装中的合作行为引起的。这些结果表明，类似的匹配/错配效应可能在其他类别的对映选择性双催化光化学反应中很重要。
Stereoinduction in complex organic reactions often involves the influence of multiple stereocontrol elements. The interaction among these can often result in the observation of significant cooperative effects that afford different rates and selectivities between the matched and mismatched sets of stereodifferentiating chiral elements. The elucidation of matched/mismatched effects in ground-state chemical reactions was a critically important theme in the maturation of modern stereocontrolled synthesis. The development of robust methods for the control of photochemical reactions, however, is a relatively recent development, and similar cooperative stereocontrolling effects in excited-state enantioselective photoreactions have not previously been documented. Herein, we describe a tandem chiral photocatalyst/Brønsted acid strategy for highly enantioselective [2+2] photocycloadditions of vinyl pyridines. Importantly, the matched and mismatched chiral catalyst pairs exhibit different reaction rates and enantioselectivities across a range of coupling partners. We observe no evidence of ground-state interactions between the photocatalysts and conclude that these effects arise from their cooperative behavior in a transient excited-state assembly. These results suggest that similar matched/mismatched effects might be important in other classes of enantioselective dual-catalytic photochemical reactions.
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影响因子：
62.1
作者：
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