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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
KeywordAsymmetric Sulfoxidation Manganese Heteroaromatic Sulfides Porphyrin-like Cation Radical
Source PublicationACS CATALYSIS
2017-07-01
DOI10.1021/acscatal.7b00968
Volume7Issue:7Pages:4890-4895
Indexed BySCI
SubtypeArticle
WOS HeadingsScience & Technology ; Physical Sciences
WOS SubjectChemistry, Physical
WOS Research AreaChemistry
WOS KeywordAQUEOUS HYDROGEN-PEROXIDE ; ASYMMETRIC OXIDATION ; CHIRAL SULFOXIDES ; TERMINAL OXIDANT ; COMPLEX ; EPOXIDATION ; H2O2 ; MONOOXYGENASES ; ACTIVATION ; REACTIVITY
AbstractA 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.
Language英语
WOS IDWOS:000405360800083
Citation statistics
Cited Times:8[WOS]   [WOS Record]     [Related Records in WOS]
Document Type期刊论文
Identifierhttp://cas-ir.dicp.ac.cn/handle/321008/149813
Collection中国科学院大连化学物理研究所
Affiliation1.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
GB/T 7714
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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