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题名: Highly Chemoselective and Enantioselective Catalytic Oxidation of Heteroaromatic Sulfides via High-Valent Manganese(IV)-Oxo Cation Radical Oxidizing Intermediates
作者: 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
发表日期: 2017-07-01
DOI: 10.1021/acscatal.7b00968
卷: 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
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.
关键词[WOS]: AQUEOUS HYDROGEN-PEROXIDE ;  ASYMMETRIC OXIDATION ;  CHIRAL SULFOXIDES ;  TERMINAL OXIDANT ;  COMPLEX ;  EPOXIDATION ;  H2O2 ;  MONOOXYGENASES ;  ACTIVATION ;  REACTIVITY
语种: 英语
WOS记录号: WOS:000405360800083
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/149813
Appears in Collections:中国科学院大连化学物理研究所_期刊论文

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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

Recommended Citation:
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.
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