Hydrogen Bonding-Assisted and Nonheme Manganese-Catalyzed Remote Hydroxylation of C-H Bonds in Nitrogen-Containing Molecules

被引:44
作者
Chen, Jie [3 ]
Song, Wenxun [3 ]
Yao, Jinping [3 ]
Wu, Zhimin [1 ]
Lee, Yong-Min [2 ]
Wang, Yong [1 ]
Nam, Wonwoo [2 ]
Wang, Bin [3 ]
机构
[1] Ningbo Univ, Inst Drug Discovery Technol, Ningbo 315211, Peoples R China
[2] Ewha Womans Univ, Dept Chem & Nano Sci, Seoul 03760, South Korea
[3] Univ Jinan, Sch Chem & Chem Engn, Jinan 250022, Peoples R China
基金
中国国家自然科学基金;
关键词
ALIPHATIC-AMINES; OXIDATION; ACID; IRON; HEXAFLUOROISOPROPANOL; ACTIVATION; OXYFUNCTIONALIZATION; FUNCTIONALIZATION; H2O2; OXYGENATION;
D O I
10.1021/jacs.2c13832
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The development of catalytic systems capable of oxygenating unactivated C-H bonds with excellent site-selectivity and functional group tolerance under mild conditions remains a challenge. Inspired by the secondary coordination sphere (SCS) hydrogen bonding in metallooxygenases, reported herein is an SCS solvent hydrogen bonding strategy that employs 1,1,1,3,3,3hexafluoroisopropanol (HFIP) as a strong hydrogen bond donor solvent to enable remote C-H hydroxylation in the presence of basic aza-heteroaromatic rings with a low loading of a readily available and inexpensive manganese complex as a catalyst and hydrogen peroxide as a terminal oxidant. We demonstrate that this strategy represents a promising compliment to the current state-of-the-art protection approaches that rely on precomplexation with strong Lewis and/or Bronsted acids. Mechanistic studies with experimental and theoretical approaches reveal the existence of a strong hydrogen bonding between the nitrogen-containing substrate and HFIP, which prevents the catalyst deactivation by nitrogen binding and deactivates the basic nitrogen atom toward oxygen atom transfer and the alpha-C-H bonds adjacent to the nitrogen center toward H-atom abstraction. Moreover, the hydrogen bonding exerted by HFIP has also been demonstrated not only to facilitate the O-O bond heterolytic cleavage of a putative MnIII-OOH precursor to generate MnV(O)(OC(O)CH2Br) as an active oxidant but also to affect the stability and the activity of MnV(O)(OC(O)CH2Br).
引用
收藏
页码:5456 / 5466
页数:11
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