Mechanism and Chemoselectivity of Mn-Catalyzed Intramolecular Nitrene Transfer Reaction: C-H Amination vs. C=C Aziridination
被引:6
作者:
Wang, Juping
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机构:
Guangdong Pharmaceut Univ, Dept Pharmaceut Engn, Guangzhou 510006, Peoples R ChinaGuangdong Pharmaceut Univ, Dept Pharmaceut Engn, Guangzhou 510006, Peoples R China
Wang, Juping
[1
]
Zheng, Kangcheng
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机构:
Sun Yat Sen Univ, Sch Chem, Guangzhou 510275, Guangdong, Peoples R ChinaGuangdong Pharmaceut Univ, Dept Pharmaceut Engn, Guangzhou 510006, Peoples R China
Zheng, Kangcheng
[2
]
Li, Ting
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Guangdong Pharmaceut Univ, Dept Pharmaceut Engn, Guangzhou 510006, Peoples R ChinaGuangdong Pharmaceut Univ, Dept Pharmaceut Engn, Guangzhou 510006, Peoples R China
Li, Ting
[1
]
Zhan, Xiaojing
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机构:
Guangdong Pharmaceut Univ, Dept Pharmaceut Engn, Guangzhou 510006, Peoples R ChinaGuangdong Pharmaceut Univ, Dept Pharmaceut Engn, Guangzhou 510006, Peoples R China
Zhan, Xiaojing
[1
]
机构:
[1] Guangdong Pharmaceut Univ, Dept Pharmaceut Engn, Guangzhou 510006, Peoples R China
[2] Sun Yat Sen Univ, Sch Chem, Guangzhou 510275, Guangdong, Peoples R China
mechanism;
chemoselectivity;
C-H amination;
C=C aziridination;
manganese;
C(SP(3))-H BOND AMINATION;
TRANSFER CHEMISTRY;
INSIGHT;
SELECTIVITY;
RUTHENIUM;
AZIDES;
IMIDO;
D O I:
10.3390/catal10030292
中图分类号:
O64 [物理化学(理论化学)、化学物理学];
学科分类号:
070304 ;
081704 ;
摘要:
The reactivity, mechanism and chemoselectivity of the Mn-catalyzed intramolecular C-H amination versus C=C aziridination of allylic substrate cis-4-hexenylsulfamate are investigated by BP86 density functional theory computations. Emphasis is placed on the origins of high reactivity and high chemoselectivity of Mn catalysis. The N p orbital character of frontier orbitals, a strong electron-withdrawing porphyrazine ligand and a poor pi backbonding of high-valent Mn-III metal to N atom lead to high electrophilic reactivity of Mn-nitrene. The calculated energy barrier of C-H amination is 9.9 kcal/mol lower than that of C=C aziridination, which indicates that Mn-based catalysis has an excellent level of chemoselectivity towards C-H amination, well consistent with the experimental the product ratio of amintion-to-aziridination I:A (i.e., (Insertion):(Aziridination)) >20:1. This extraordinary chemoselectivity towards C-H amination originates from the structural features of porphyrazine: a rigid ligand with the big pi-conjugated bond. Electron-donating substituents can further increase Mn-catalyzed C-H amination reactivity. The controlling factors found in this work may be considered as design elements for an economical and environmentally friendly C-H amination system with high reactivity and high chemoselectivity.
机构:
Kyushu Univ, Dept Chem, Fac Sci, Grad Sch,Higashi Ku, Fukuoka 8128581, Japan
Kyushu Univ, Int Inst Carbon Neutral Energy Res, Higashi Ku, Fukuoka 8128581, JapanKyushu Univ, Dept Chem, Fac Sci, Grad Sch,Higashi Ku, Fukuoka 8128581, Japan
Ichinose, Masami
Suematsu, Hidehiro
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机构:
Kyushu Univ, Dept Chem, Fac Sci, Grad Sch,Higashi Ku, Fukuoka 8128581, Japan
Kyushu Univ, Int Inst Carbon Neutral Energy Res, Higashi Ku, Fukuoka 8128581, JapanKyushu Univ, Dept Chem, Fac Sci, Grad Sch,Higashi Ku, Fukuoka 8128581, Japan
Suematsu, Hidehiro
Yasutomi, Yoichi
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机构:
Kyushu Univ, Dept Chem, Fac Sci, Grad Sch,Higashi Ku, Fukuoka 8128581, Japan
Kyushu Univ, Int Inst Carbon Neutral Energy Res, Higashi Ku, Fukuoka 8128581, JapanKyushu Univ, Dept Chem, Fac Sci, Grad Sch,Higashi Ku, Fukuoka 8128581, Japan
Yasutomi, Yoichi
Nishioka, Yota
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机构:
Kyushu Univ, Dept Chem, Fac Sci, Grad Sch,Higashi Ku, Fukuoka 8128581, Japan
Kyushu Univ, Int Inst Carbon Neutral Energy Res, Higashi Ku, Fukuoka 8128581, JapanKyushu Univ, Dept Chem, Fac Sci, Grad Sch,Higashi Ku, Fukuoka 8128581, Japan
Nishioka, Yota
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机构:
Uchida, Tatsuya
Katsuki, Tsutomu
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机构:
Kyushu Univ, Dept Chem, Fac Sci, Grad Sch,Higashi Ku, Fukuoka 8128581, Japan
Kyushu Univ, Int Inst Carbon Neutral Energy Res, Higashi Ku, Fukuoka 8128581, JapanKyushu Univ, Dept Chem, Fac Sci, Grad Sch,Higashi Ku, Fukuoka 8128581, Japan
机构:
Univ Hong Kong, Dept Chem, State Key Lab Synthet Chem, Hong Kong, Peoples R China
Shanghai Inst Organ Chem, Shanghai Hong Kong Joint Lab Chem Synth, 354 Feng Lin Rd, Shanghai, Peoples R ChinaUniv Hong Kong, Dept Chem, State Key Lab Synthet Chem, Hong Kong, Peoples R China
Du, Yi-Dan
Zhou, Cong-Ying
论文数: 0引用数: 0
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机构:
Univ Hong Kong, Dept Chem, State Key Lab Synthet Chem, Hong Kong, Peoples R China
Jinan Univ, Coll Chem & Mat Sci, Guangzhou, Peoples R ChinaUniv Hong Kong, Dept Chem, State Key Lab Synthet Chem, Hong Kong, Peoples R China
Zhou, Cong-Ying
To, Wai-Pong
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机构:
Univ Hong Kong, Dept Chem, State Key Lab Synthet Chem, Hong Kong, Peoples R ChinaUniv Hong Kong, Dept Chem, State Key Lab Synthet Chem, Hong Kong, Peoples R China
To, Wai-Pong
Wang, Hai-Xu
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机构:
Univ Hong Kong, Dept Chem, State Key Lab Synthet Chem, Hong Kong, Peoples R ChinaUniv Hong Kong, Dept Chem, State Key Lab Synthet Chem, Hong Kong, Peoples R China
Wang, Hai-Xu
Che, Chi-Ming
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机构:
Univ Hong Kong, Dept Chem, State Key Lab Synthet Chem, Hong Kong, Peoples R China
HKU Shenzhen Inst Res & Innovat, Shenzhen, Peoples R China
Shanghai Inst Organ Chem, Shanghai Hong Kong Joint Lab Chem Synth, 354 Feng Lin Rd, Shanghai, Peoples R ChinaUniv Hong Kong, Dept Chem, State Key Lab Synthet Chem, Hong Kong, Peoples R China
机构:
Kyushu Univ, Dept Chem, Fac Sci, Grad Sch,Higashi Ku, Fukuoka 8128581, Japan
Kyushu Univ, Int Inst Carbon Neutral Energy Res, Higashi Ku, Fukuoka 8128581, JapanKyushu Univ, Dept Chem, Fac Sci, Grad Sch,Higashi Ku, Fukuoka 8128581, Japan
Ichinose, Masami
Suematsu, Hidehiro
论文数: 0引用数: 0
h-index: 0
机构:
Kyushu Univ, Dept Chem, Fac Sci, Grad Sch,Higashi Ku, Fukuoka 8128581, Japan
Kyushu Univ, Int Inst Carbon Neutral Energy Res, Higashi Ku, Fukuoka 8128581, JapanKyushu Univ, Dept Chem, Fac Sci, Grad Sch,Higashi Ku, Fukuoka 8128581, Japan
Suematsu, Hidehiro
Yasutomi, Yoichi
论文数: 0引用数: 0
h-index: 0
机构:
Kyushu Univ, Dept Chem, Fac Sci, Grad Sch,Higashi Ku, Fukuoka 8128581, Japan
Kyushu Univ, Int Inst Carbon Neutral Energy Res, Higashi Ku, Fukuoka 8128581, JapanKyushu Univ, Dept Chem, Fac Sci, Grad Sch,Higashi Ku, Fukuoka 8128581, Japan
Yasutomi, Yoichi
Nishioka, Yota
论文数: 0引用数: 0
h-index: 0
机构:
Kyushu Univ, Dept Chem, Fac Sci, Grad Sch,Higashi Ku, Fukuoka 8128581, Japan
Kyushu Univ, Int Inst Carbon Neutral Energy Res, Higashi Ku, Fukuoka 8128581, JapanKyushu Univ, Dept Chem, Fac Sci, Grad Sch,Higashi Ku, Fukuoka 8128581, Japan
Nishioka, Yota
论文数: 引用数:
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机构:
Uchida, Tatsuya
Katsuki, Tsutomu
论文数: 0引用数: 0
h-index: 0
机构:
Kyushu Univ, Dept Chem, Fac Sci, Grad Sch,Higashi Ku, Fukuoka 8128581, Japan
Kyushu Univ, Int Inst Carbon Neutral Energy Res, Higashi Ku, Fukuoka 8128581, JapanKyushu Univ, Dept Chem, Fac Sci, Grad Sch,Higashi Ku, Fukuoka 8128581, Japan
机构:
Univ Hong Kong, Dept Chem, State Key Lab Synthet Chem, Hong Kong, Peoples R China
Shanghai Inst Organ Chem, Shanghai Hong Kong Joint Lab Chem Synth, 354 Feng Lin Rd, Shanghai, Peoples R ChinaUniv Hong Kong, Dept Chem, State Key Lab Synthet Chem, Hong Kong, Peoples R China
Du, Yi-Dan
Zhou, Cong-Ying
论文数: 0引用数: 0
h-index: 0
机构:
Univ Hong Kong, Dept Chem, State Key Lab Synthet Chem, Hong Kong, Peoples R China
Jinan Univ, Coll Chem & Mat Sci, Guangzhou, Peoples R ChinaUniv Hong Kong, Dept Chem, State Key Lab Synthet Chem, Hong Kong, Peoples R China
Zhou, Cong-Ying
To, Wai-Pong
论文数: 0引用数: 0
h-index: 0
机构:
Univ Hong Kong, Dept Chem, State Key Lab Synthet Chem, Hong Kong, Peoples R ChinaUniv Hong Kong, Dept Chem, State Key Lab Synthet Chem, Hong Kong, Peoples R China
To, Wai-Pong
Wang, Hai-Xu
论文数: 0引用数: 0
h-index: 0
机构:
Univ Hong Kong, Dept Chem, State Key Lab Synthet Chem, Hong Kong, Peoples R ChinaUniv Hong Kong, Dept Chem, State Key Lab Synthet Chem, Hong Kong, Peoples R China
Wang, Hai-Xu
Che, Chi-Ming
论文数: 0引用数: 0
h-index: 0
机构:
Univ Hong Kong, Dept Chem, State Key Lab Synthet Chem, Hong Kong, Peoples R China
HKU Shenzhen Inst Res & Innovat, Shenzhen, Peoples R China
Shanghai Inst Organ Chem, Shanghai Hong Kong Joint Lab Chem Synth, 354 Feng Lin Rd, Shanghai, Peoples R ChinaUniv Hong Kong, Dept Chem, State Key Lab Synthet Chem, Hong Kong, Peoples R China