Citation: Yang Yinuo, Zhang Qi, Shi Jing, Fu Yao. Mechanism Study of Mn(I) Complex-catalyzed Imines and Alkynes Dehydrogenation Coupling Reaction[J]. Acta Chimica Sinica, ;2016, 74(5): 422-428. doi: 10.6023/A15110736 shu

Mechanism Study of Mn(I) Complex-catalyzed Imines and Alkynes Dehydrogenation Coupling Reaction

Yang Yinuo ,
Zhang Qi ,
Shi Jing ^*,, ,
Fu Yao ^*,,

1.
Department of Chemistry, University of Science and Technology of China, Hefei 230026

Corresponding author: Shi Jing, shijing@ustc.edu.cn Fu Yao, fuyao@ustc.edu.cn
Received Date: 21 November 2015

Fund Project: Fundamental Research Funds for the Central Universities WK2060190025the National Natural Science Foundation of China 21325208Fundamental Research Funds for the Central Universities FRF-TP-14-015A2the National Natural Science Foundation of China 21361140372the National Natural Science Foundation of China 21202006973 Program 2012CB215306Science Foundation of The Chinese Academy of Sciences KJCX2-EW-J02the National Natural Science Foundation of China 21172209Fundamental Research Funds for the Central Universities WK2060190040

Figures(6)

With the development and widespread use of transition metal catalysts, C—H activation has become a hot topic in organic synthesis, especially in the construction of C—C bond of organic compounds. As an important and cheap catalyst, manganese complex has shown great potential for catalyzing C—H activation both in academic and industrial applications. In this paper, the mechanism of manganese-catalyzed dehydrogenative [4+2] annulation by C—H/N—H activation was investigated systematically with the aid of density functional theory (DFT) calculations in 1, 4-dioxane solvent. In detail, we use M06-L/[SDD:6-311+G(d, p)(SMD)]//M06-L/[LANL2DZ:6-31G(d)] to examine the Gibbs free energy, structure and other properties of possible intermediates and transition states in this catalytic cycle. By comprehensive comparison and discussion, we obtained a favorable pathway consisting of five steps: (1) catalyst initiation occurred with the assistance of bromine anion rather than imide to form active catalyst; (2) alkyne inserted into the active catalyst to generate a seven-membered manganacycle after dissociation of a carbon monoxide; (3) double bond migration happened in this seven-membered manganacycle to form a product precursor; (4) the product precursor would dissociate by β-H elimination and generated product isoquinoline and active Mn—H complex; (5) the active Mn—H complex was subsequently combined with an imine followed by dehydrogenative C—H activation to complete the whole catalytic cycle. In this context, the reason for the highly atom-economical C—H activation by direct dehydrogenation (eliminates the necessity for oxidants or additives) has been clarified by this mechanism. The present study was aimed at further understanding of Mn(I)-catalyzed dehydrogenative C—H activation, and provided more theoretical basis for future more Mn-catalyzed C—H activation.
- manganese-catalyzed,
- density functional theory (DFT),
- C—H activation,
- mechanism
1. [1]
  Wencel-Delord, J.; Glorious, F. Nat. Chem. 2013, 5, 369. (b) Ackermann, L. Chem. Rev. 2011, 111, 1315. (c) Yeung, C. S.; Dong, V. M. Chem. Rev. 2011, 111, 1215. (d) Gutekunst, W. R.; Baran, P. S. Chem. Soc. Rev. 2011, 40, 1976. (e) Iwai, T.; Sawamura, M. ACS Catal. 2015, 5, 5031. (f) Segawa, Y.; Maekawa, T.; Itami, K. Angew. Chem., Int. Ed. 2015, 54, 66. (g) Topczewski, J. J.; Sanford, M. S. Chem. Sci. 2015, 6, 70. (h) Liao, G.; Shi, B. Acta Chim. Sinica 2015, 73, 1283. (廖港, 史炳锋, 化学学报, 2015, 73, 1283.) (i) Zhou, L.; Lu, W. Acta Chim. Sinica 2015, 73, 1250. (周励宏, 陆文军, 化学学报, 2015, 73, 1250.) (j) Zhao, J.; Zhang, Q. Acta Chim. Sinica 2015, 73, 1235. (赵金钵, 张前, 化学学报, 2015, 73, 1235.) (k) Shang, X.; Liu, Z. Acta Chim. Sinica 2015, 73, 1275. (尚筱洁, 柳忠全, 化学学报, 2015, 73, 1275.) (l) Pan, F.; Shi, Z. Acta Chim. Sinica 2012, 70, 1679. (潘菲, 施章杰, 化学学报, 2012, 70, 1679.) (m) Zhao, H.; Sun, H.; Wang, L.; Li, X. Acta Chim. Sinica 2015, 73, 1307. (n) Qiu, H.; Zhang, D.; Liu, S.; Qiu, L.; Zhou, J.; Qian, Y.; Zhai, C.; Hu, W. Acta Chim. Sinica 2012, 70, 2484. (邱晃, 张丹, 刘顺英, 邱林, 周俊, 钱宇, 翟昌伟, 胡文浩, 化学学报, 2012, 70, 2484.)
2. [2]
  Ye, B.; Cramer, N. Acc. Chem. Res. 2015, 48, 1308. (b) Arockiam, P. B.; Bruneau, C.; Dixneuf, P. H. Chem. Rev. 2012, 112, 5879. (c) Zhang, C.; Tang, C.; Jiao, N. Chem. Soc. Rev. 2012, 41, 3464. (d) Hickman, A. J.; Sanford, M. S. Nature 2012, 484, 177. (e) Sun, C. L.; Li, B. J.; Shi, J. Z. Chem. Rev. 2011, 111, 1293. (f) Ma, Y.; Li, W.; Yu, B. Acta Chim. Sinica 2013, 71, 541. (马玉勇, 李微, 俞飚, 化学学报, 2013, 71, 541.) (g) Xu, J.; Chen, P.; Ye, J.; Liu, G. Acta Chim. Sinica 2015, 73, 1294. (徐佳斌, 陈品红, 叶金星, 刘国生, 化学学报, 2015, 73, 1294.) (h) Zhang, Q.; Lü, Y.; Li, Y.; Xiong, T.; Zhang, Q. Acta Chim. Sinica 2014, 72, 1139. (张茜, 吕允贺, 李燕, 熊涛, 张前, 化学学报, 2014, 72, 1139.) (i) Cai, H.; Li, D.; Liu, Z.; Wang, G. Acta Chim. Sinica 2013, 71, 717.
3. [3]
  Gunay, A.; Theopold, K. H. Chem. Rev. 2010, 110, 1060. doi: 10.1021/cr900269x
4. [4]
  Kuninobu, Y.; Nishina, Y.; Takeuchi, T.; Takai, K. Angew. Chem., Int. Ed. 2007, 46, 6518. doi: 10.1002/(ISSN)1521-3773
5. [5]
  Zhou, B.; Chen, H.; Wang, C. J. Am. Chem. Soc. 2013, 135, 1264. doi: 10.1021/ja311689k
6. [6]
  He, R.; Huang, Z.-T.; Zheng, Q.-Y.; Wang, C. Angew. Chem., Int. Ed. 2014, 53, 4950. doi: 10.1002/anie.201402575
7. [7]
  Zhou, B.; Chen, H.; Wang, C. J. Am. Chem. Soc. 2013, 135, 1264. doi: 10.1021/ja311689k
8. [8]
  Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Jr. Montgomery, J. A.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Keith, T.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, O.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian 09, Revision B. 01, Gaussian, Inc., Wallingford CT, 2010
9. [9]
  Zhao, Y.; Truhlar, D. G. J. Chem. Phys. 2006, 125, 194101. doi: 10.1063/1.2370993
10. [10]
  Wadt, W. R.; Hay, P. J. J. Chem. Phys. 1985, 82, 284. doi: 10.1063/1.448800
11. [11]
  Fukui, K. Acc. Chem. Res. 1981, 14, 363. (b) Fukui, K. J. Phys. Chem. 1970, 74, 4161.
12. [12]
  Marenich, A. V.; Cramer, C. J.; Truhlar, D. G. J. Phys. Chem. B 2009, 113, 6378. doi: 10.1021/jp810292n
13. [13]
  Fuentealba, P.; Preuss, H.; Stoll, H.; Vonszentpaly, L. Chem. Phys. Lett. 1982, 89, 418. doi: 10.1016/0009-2614(82)80012-2
14. [14]
  Lan, Y.; Liu, P.; Newman, S. G.; Lautens, M.; Houk, K. N. Chem. Sci. 2012, 3, 1987. (b) Yu, H.; Fu, Y. Chem. Eur. J. 2012, 18, 16765. (c) Ford, D. D.; Nielsen, L. P. C.; Zuend, S. J.; Musgrave, C. B.; Jacobsen, E. N. J. Am. Chem. Soc. 2013, 135, 15595. (d) Suresh, C. H.; Sayyed, F. B. J. Phys. Chem. A 2013, 117, 10455. (e) Yi, J.; Lu, X.; Sun, Y.-Y.; Xiao, B.; Liu, L. Angew. Chem., Int. Ed. 2013, 52, 12409. (f) Zhang, S. L.; Shi, L.; Ding, Y. Q. J. Am. Chem. Soc. 2011, 133, 20218. (g) Proutiere, F.; Aufiero, M.; Schoenebeck, F. J. Am. Chem. Soc. 2012, 134, 606.
15. [15]
  Xie, H.; Lin, Z. Organometallics 2014, 33, 892; (b) Schoenebeck, F.; Houk, K. N. J. Am. Chem. Soc. 2010, 132, 2496; (c) Ariafard, A.; Brookes, N. J.; Stanger, R.; Yates, B. F. Organometallics 2011, 30, 1340.
1. [1]
  Yingchun ZHANG , Yiwei SHI , Ruijie YANG , Xin WANG , Zhiguo SONG , Min WANG . Dual ligands manganese complexes based on benzene sulfonic acid and 2, 2′-bipyridine: Structure and catalytic properties and mechanism in Mannich reaction. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1501-1510. doi: 10.11862/CJIC.20240078
2. [2]
  Xinyu Yin , Haiyang Shi , Yu Wang , Xuefei Wang , Ping Wang , Huogen Yu . Spontaneously Improved Adsorption of H₂O and Its Intermediates on Electron-Deficient Mn^(3+δ)+ for Efficient Photocatalytic H₂O₂ Production. Acta Physico-Chimica Sinica, 2024, 40(10): 2312007-. doi: 10.3866/PKU.WHXB202312007
3. [3]
  Tong Zhou , Xue Liu , Liang Zhao , Mingtao Qiao , Wanying Lei . Efficient Photocatalytic H₂O₂ Production and Cr(VI) Reduction over a Hierarchical Ti₃C₂/In₄SnS₈ Schottky Junction. Acta Physico-Chimica Sinica, 2024, 40(10): 2309020-. doi: 10.3866/PKU.WHXB202309020
4. [4]
  Xingyang LI , Tianju LIU , Yang GAO , Dandan ZHANG , Yong ZHOU , Meng PAN . A superior methanol-to-propylene catalyst: Construction via synergistic regulation of pore structure and acidic property of high-silica ZSM-5 zeolite. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1279-1289. doi: 10.11862/CJIC.20240026
5. [5]
  Shaojie Ding , Henan Wang , Xiaojing Dai , Yuru Lv , Xinxin Niu , Ruilian Yin , Fangfang Wu , Wenhui Shi , Wenxian Liu , Xiehong Cao . Mn-modulated Co–N–C oxygen electrocatalysts for robust and temperature-adaptative zinc-air batteries. Chinese Journal of Structural Chemistry, 2024, 43(7): 100302-100302. doi: 10.1016/j.cjsc.2024.100302
6. [6]
  Wenjiang LI , Pingli GUAN , Rui YU , Yuansheng CHENG , Xianwen WEI . C₆₀-MoP-C nanoflowers van der Waals heterojunctions and its electrocatalytic hydrogen evolution performance. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 771-781. doi: 10.11862/CJIC.20230289
7. [7]
  Tong Li , Leping Pan , Yan Zhang , Jihu Su , Kai Li , Kuiliang Li , Hu Chen , Qi Sun , Zhiyong Wang . Electrochemical construction of 2,5-diaryloxazoles via N–H and C(sp³)-H functionalization. Chinese Chemical Letters, 2024, 35(4): 108897-. doi: 10.1016/j.cclet.2023.108897
8. [8]
  Guangming YIN , Huaiyao WANG , Jianhua ZHENG , Xinyue DONG , Jian LI , Yi'nan SUN , Yiming GAO , Bingbing WANG . Preparation and photocatalytic degradation performance of Ag/protonated g-C₃N₄ nanorod materials. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1491-1500. doi: 10.11862/CJIC.20240086
9. [9]
  Min WANG , Dehua XIN , Yaning SHI , Wenyao ZHU , Yuanqun ZHANG , Wei ZHANG . Construction and full-spectrum catalytic performance of multilevel Ag/Bi/nitrogen vacancy g-C₃N₄/Ti₃C₂T_x Schottky junction. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1123-1134. doi: 10.11862/CJIC.20230477
10. [10]
  Yi Luo , Lin Dong . Multicomponent remote C(sp²)-H bond addition by Ru catalysis: An efficient access to the alkylarylation of 2H-imidazoles. Chinese Chemical Letters, 2024, 35(10): 109648-. doi: 10.1016/j.cclet.2024.109648
11. [11]
  Ke-Ai Zhou , Lian Huang , Xing-Ping Fu , Li-Ling Zhang , Yu-Ling Wang , Qing-Yan Liu . Fluorinated metal-organic framework for methane purification from a ternary CH4/C2H6/C3H8 mixture. Chinese Journal of Structural Chemistry, 2023, 42(11): 100172-100172. doi: 10.1016/j.cjsc.2023.100172
12. [12]
  Shulei Hu , Yu Zhang , Xiong Xie , Luhan Li , Kaixian Chen , Hong Liu , Jiang Wang . Rh(Ⅲ)-catalyzed late-stage C-H alkenylation and macrolactamization for the synthesis of cyclic peptides with unique Trp(C7)-alkene crosslinks. Chinese Chemical Letters, 2024, 35(8): 109408-. doi: 10.1016/j.cclet.2023.109408
13. [13]
  Haoran Shi , Jiaxin Wang , Yuqin Zhu , Hongyang Li , Guodong Ju , Lanlan Zhang , Chao Wang . Highly selective α-C(sp³)-H arylation of alkenyl amides via nickel chain-walking catalysis. Chinese Chemical Letters, 2024, 35(7): 109333-. doi: 10.1016/j.cclet.2023.109333
14. [14]
  Jingping Hu , Jing Xu . Total synthesis of a putative yuzurimine-type Daphniphyllum alkaloid C₁₄–epi-deoxycalyciphylline H. Chinese Chemical Letters, 2024, 35(4): 108733-. doi: 10.1016/j.cclet.2023.108733
15. [15]
  Yujia Shi , Yan Qiao , Pengfei Xie , Miaomiao Tian , Xingwei Li , Junbiao Chang , Bingxian Liu . Rhodium-catalyzed enantioselective in situ C(sp³)−H heteroarylation by a desymmetrization approach. Chinese Chemical Letters, 2024, 35(10): 109544-. doi: 10.1016/j.cclet.2024.109544
16. [16]
  Xiaosong PU , Hangkai WU , Taohong LI , Huijuan LI , Shouqing LIU , Yuanbo HUANG , Xuemei LI . Adsorption performance and removal mechanism of Cd(Ⅱ) in water by magnesium modified carbon foam. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1537-1548. doi: 10.11862/CJIC.20240030
17. [17]
  Dong-Xue Jiao , Hui-Li Zhang , Chao He , Si-Yu Chen , Ke Wang , Xiao-Han Zhang , Li Wei , Qi Wei . Layered (C5H6ON)2[Sb2O(C2O4)3] with a large birefringence derived from the uniform arrangement of π-conjugated units. Chinese Journal of Structural Chemistry, 2024, 43(6): 100304-100304. doi: 10.1016/j.cjsc.2024.100304
18. [18]
  Pengfei Zhang , Qingxue Ma , Zhiwei Jiang , Xiaohua Xu , Zhong Jin . Transition-metal-catalyzed remote meta-C—H alkylation and alkynylation of aryl sulfonic acids enabled by an indolyl template. Chinese Chemical Letters, 2024, 35(8): 109361-. doi: 10.1016/j.cclet.2023.109361
19. [19]
  Yuemin Chen , Yunqi Wu , Guoao Wang , Feihu Cui , Haitao Tang , Yingming Pan . Electricity-driven enantioselective cross-dehydrogenative coupling of two C(sp³)-H bonds enabled by organocatalysis. Chinese Chemical Letters, 2024, 35(9): 109445-. doi: 10.1016/j.cclet.2023.109445
20. [20]
  Kexin Dong , Chuqi Shen , Ruyu Yan , Yanping Liu , Chunqiang Zhuang , Shijie Li . Integration of Plasmonic Effect and S-Scheme Heterojunction into Ag/Ag₃PO₄/C₃N₅ Photocatalyst for Boosted Photocatalytic Levofloxacin Degradation. Acta Physico-Chimica Sinica, 2024, 40(10): 2310013-. doi: 10.3866/PKU.WHXB202310013

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(1709)
HTML views(438)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142