对映选择合成
化学
超分子化学
分子内力
激发态
合成生物学
对映体
基质(水族馆)
组合化学
立体化学
分子
有机化学
催化作用
生物信息学
物理
地质学
海洋学
生物
核物理学
作者
Ningning Sun,Hua Yin,Junyi Qian,Tai‐Ping Zhou,Juan Guo,Langyu Tang,Wentao Zhang,Yaming Deng,Weining Zhao,Guojiao Wu,Rong‐Zhen Liao,Xi Chen,Fangrui Zhong,Yuzhou Wu
出处
期刊:Nature
[Springer Nature]
日期:2022-09-21
卷期号:611 (7937): 715-720
被引量:98
标识
DOI:10.1038/s41586-022-05342-4
摘要
Naturally evolved enzymes, despite their astonishingly large variety and functional diversity, operate predominantly through thermochemical activation. Integrating prominent photocatalysis modes into proteins, such as triplet energy transfer, could create artificial photoenzymes that expand the scope of natural biocatalysis1–3. Here, we exploit genetically reprogrammed, chemically evolved photoenzymes embedded with a synthetic triplet photosensitizer that are capable of excited-state enantio-induction4–6. Structural optimization through four rounds of directed evolution afforded proficient variants for the enantioselective intramolecular [2+2]-photocycloaddition of indole derivatives with good substrate generality and excellent enantioselectivities (up to 99% enantiomeric excess). A crystal structure of the photoenzyme–substrate complex elucidated the non-covalent interactions that mediate the reaction stereochemistry. This study expands the energy transfer reactivity7–10 of artificial triplet photoenzymes in a supramolecular protein cavity and unlocks an integrated approach to valuable enantioselective photochemical synthesis that is not accessible with either the synthetic or the biological world alone. Triplet photoenzymes developed through genetic encoding and directed evolution result in excited-state photocatalysts that provide a valuable approach to enantioselective photochemical synthesis.
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