通过铀光催化对苄基衍生基团进行脱保护

IF 2.5 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Organometallics Pub Date : 2024-04-01 DOI:10.1021/acs.organomet.4c00080
Jiaolong Meng, Lei Ji, Xuefeng Jiang
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引用次数: 0

摘要

为了规避与易燃/易爆氢气相关的危险,并解决还原体系中的底物兼容性问题,我们开发了一种温和的方法,在环境条件下的可见光照射下,通过铀促进苄基脱保护。作为一种金属氧型光敏剂,铀氧物种与湿气相容,通过配体-金属电荷转移(LMCT)激发实现苄基 C-H 活化。随后,大气中的氧气捕获苄基自由基,诱导苄基位置发生氧化。在酸性条件下,半缩醛发生脱落,导致 C-O 键裂解。这种方法的特点是条件温和,操作方便,与湿气和氧气兼容。它为药物和有机材料的合成提供了一种苄基脱保护的补充策略。
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Deprotection of Benzyl-Derived Groups via Uranyl-Photocatalysis
To circumvent the hazards associated with flammable/explosive hydrogen and address substrate compatibility issues in reductive systems, we developed a mild method for benzyl deprotection facilitated by uranium under visible light irradiation at ambient conditions. The uranium-oxo species, as a metal-oxo-type photosensitizer, demonstrates compatibility with moisture, enabling benzyl C–H activation through ligand-to-metal charge transfer (LMCT) excitation. Subsequent capture of the benzyl radical by atmospheric oxygen induces oxidation at the benzylic position. Removal of the semiacetal occurs, resulting in C–O bond cleavage under acidic conditions. This methodology, featuring mild conditions and operational convenience, is compatible with moisture and oxygen. It presents a complementary strategy for benzyl deprotection for the synthesis of pharmaceuticals and organic materials.
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来源期刊
Organometallics
Organometallics 化学-无机化学与核化学
CiteScore
5.60
自引率
7.10%
发文量
382
审稿时长
1.7 months
期刊介绍: Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.
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