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Highly Chemoselective and Enantioselective Catalytic Oxidation of Heteroaromatic Sulfides via High-Valent Manganese(IV)-Oxo Cation Radical Oxidizing Intermediates
Dai, Wen1,2; Shang, Sensen1,2; Lv, Ying1,2; Li, Guosong1,2; Li, Chunsen3,4; Gao, Shuang1,2
关键词Asymmetric Sulfoxidation Manganese Heteroaromatic Sulfides Porphyrin-like Cation Radical
刊名ACS CATALYSIS
2017-07-01
DOI10.1021/acscatal.7b00968
7期:7页:4890-4895
收录类别SCI
文章类型Article
WOS标题词Science & Technology ; Physical Sciences
类目[WOS]Chemistry, Physical
研究领域[WOS]Chemistry
关键词[WOS]AQUEOUS HYDROGEN-PEROXIDE ; ASYMMETRIC OXIDATION ; CHIRAL SULFOXIDES ; TERMINAL OXIDANT ; COMPLEX ; EPOXIDATION ; H2O2 ; MONOOXYGENASES ; ACTIVATION ; REACTIVITY
英文摘要A manganese complex with a porphyrin-like ligand that catalyzes the highly chemoselective and enantioselective oxidation of heteroaromatic sulfides, including imidazole, benzimidazole, indole, pyridine, pyrimidine, pyrazine, sym-triazine, thiophene, thiazole, benzothiazole, and benzoxazole, with hydrogen peroxide is described, furnishing the corresponding sulfoxides in good to excellent yields and enantioselectivities (up to 90% yield and up to >99% ee) within a short reaction time (0.5 h). The practical utility of the method has been demonstrated in the gram-scale synthesis of chiral sulfoxide. Mechanistic studies, performed with O-18-labeled water ((H2O)-O-18), hydrogen peroxide ((H2O2)-O-18), and cumyl hydroperoxide, reveal that a high-valent manganese-oxo species is generated as the oxygen atom delivering agent via carboxylic acid assisted heterolysis of O-O bonds. Density functional theory (DFT) calculations were also carried out to give further insight into the mechanism of manganese-catalyzed sulfoxidation. On the basis of the theoretical study, the coupled high-valent manganese(IV)-oxo cation radical species, which bears obvious similarities with that of reactive intermediates in the catalytic oxygenation reactions based on the cytochrome P450 and metalloporphyrin models, has been proposed as the reactive oxidant in the non-heme manganese catalyst system.
语种英语
WOS记录号WOS:000405360800083
引用统计
被引频次:7[WOS]   [WOS记录]     [WOS相关记录]
文献类型期刊论文
条目标识符http://cas-ir.dicp.ac.cn/handle/321008/149813
专题中国科学院大连化学物理研究所
作者单位1.Chinese Acad Sci, Dalian Inst Chem Phys, Dalian 116023, Peoples R China
2.Dalian Natl Lab Clean Energy, Dalian 116023, Peoples R China
3.Chinese Acad Sci, Fujian Inst Res Struct Matter, State Key Lab Struct Chem, Fuzhou 350002, Fujian, Peoples R China
4.Fujian Prov Key Lab Theoret & Computat Chem, Xiamen 361005, Fujian, Peoples R China
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Dai, Wen,Shang, Sensen,Lv, Ying,et al. Highly Chemoselective and Enantioselective Catalytic Oxidation of Heteroaromatic Sulfides via High-Valent Manganese(IV)-Oxo Cation Radical Oxidizing Intermediates[J]. ACS CATALYSIS,2017,7(7):4890-4895.
APA Dai, Wen,Shang, Sensen,Lv, Ying,Li, Guosong,Li, Chunsen,&Gao, Shuang.(2017).Highly Chemoselective and Enantioselective Catalytic Oxidation of Heteroaromatic Sulfides via High-Valent Manganese(IV)-Oxo Cation Radical Oxidizing Intermediates.ACS CATALYSIS,7(7),4890-4895.
MLA Dai, Wen,et al."Highly Chemoselective and Enantioselective Catalytic Oxidation of Heteroaromatic Sulfides via High-Valent Manganese(IV)-Oxo Cation Radical Oxidizing Intermediates".ACS CATALYSIS 7.7(2017):4890-4895.
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