Citation: Xiao-Si MA, Yong-Zhu ZHOU, Lei ZHANG. Theoretical Measurements of Quantitative Effects Caused by Spectator Ligands on Palladium-catalyzed C−H Activation[J]. Chinese Journal of Structural Chemistry, ;2022, 41(3): 220301. doi: 10.14102/j.cnki.0254-5861.2011-3286 shu

Theoretical Measurements of Quantitative Effects Caused by Spectator Ligands on Palladium-catalyzed C−H Activation

Xiao-Si MA ^a ,
Yong-Zhu ZHOU ^{a, b,,} ,
Lei ZHANG ^a,,

a.
Department of Chemistry, School of Science, Tianjin Chengjian University, Tianjin 300384, China
b.
School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China

Corresponding author: Yong-Zhu ZHOU, li_weihnxy@163.com Lei ZHANG, li_weihnxy@163.com
Received Date: 15 June 2021
Accepted Date: 16 August 2021

Fund Project: the National Natural Science Foundation of China 22003045the National Natural Science Foundation of China 21808156the Fundamental Research Funds for Tianjin Colleges 2018KJ171the Fundamental Research Funds for Tianjin Colleges 2017KJ064

Figures(11)

Ligands can definitely influence C−H activation at the metal center. A ligand not directly participating in the reaction is called a spectator ligand. We attempt to quantitatively characterize the effects of diverse spectator ligands on C−H activation at palladium. We designed a model palladium catalyst and selected an array of spectator ligands, such as methoxyl, amide, methyl, phenyl, cyanide, fluorine, chlorine, and several neutral ligands, and performed density functional theory calculations on the mechanism and energetics of C−H activation reactions of benzene with different catalysts. Univalent ligands have substantially larger effects than neutral ligands, and strongly σ-donating ligands (e.g., methyl and phenyl) severely hinder the C−H activation in progress. A ligand trans to the reaction site influences C−H activation more than that cis to the reaction site, indicating electronic effects to be at work. For example, the existence of a methyl ligand raises the barrier height of C−H activation by 6.4 or 14.4 kcal/mol when it is placed at the position cis or trans to the C−H activation site. The effects of poorly σ-donating ligands are not significant and similar to those of the κ¹-acetate ligand. Some σ-donating and π-accepting ligands, such as cyanide and isonitrile, hinder the C−H activation trans to them but appear to facilitate the C−H activation cis to them. On the basis of molecular orbital analyses, a chemical model is proposed to understand the observed ligand effects. Lastly, the conclusions are applied to explain the plausible mechanism of the dehydrogenative Heck coupling.
- C−H activation,
- ligand effect,
- palladium catalyst,
- reaction mechanism,
- DFT calculation
1. [1]
  Chen, X.; Engle, K. M.; Wang, D. H.; Yu, J. Q. Palladium(Ⅱ)-catalyzed C−H activation/C−C cross-coupling reactions: versatility and practicality. Angew. Chem. Int. Ed. 2009, 48, 5094−5115. doi: 10.1002/anie.200806273
2. [2]
  Saini, G.; Kapur, M. Palladium-catalyzed functionalizations of acidic and non-acidic C(sp³)–H bonds – recent advances. Chem. Commun. 2021, 57, 1693−1714. doi: 10.1039/D0CC06892F
3. [3]
  Chen, G.; Gong, W.; Zhuang, Z.; Andrä, M. S.; Chen, Y. Q.; Hong, X.; Yang, Y. F.; Liu, T.; Houk, K. N.; Yu, J. Q. Ligand-accelerated enantioselective methylene C(sp³)–H bond activation. Science 2016, 353, 1023–1027. doi: 10.1126/science.aaf4434
4. [4]
  Wu, C.; McCollom, S. P.; Zheng, Z. P.; Zhang, J. D.; Sha, S. C.; Li, M. Y.; Walsh, P. J.; Tomson, N. C. Aryl fluoride activation through palladium-magnesium bimetallic cooperation: a mechanistic and computational study. ACS Catal. 2020, 10, 7934–7944. doi: 10.1021/acscatal.0c01301
5. [5]
  Rocaboy, R.; Dailler, D.; Baudoin, O. A four-step synthesis of (±)-γ-lycorane via Pd⁰-catalyzed double C(sp²)–H/C(sp³)–H arylation. Org. Lett. 2018, 20, 772–775. doi: 10.1021/acs.orglett.7b03909
6. [6]
  Zhang, Q.; Shi, B. F. From reactivity and regioselectivity to stereoselectivity: an odyssey of designing PIP amine and related directing groups for C−H activation. Chin. J. Chem. 2019, 37, 647–656. doi: 10.1002/cjoc.201900090
7. [7]
  Shi, X. L.; Wang, Z. M.; Li, Y. X.; Li, X. W.; Li, X. Q.; Shi, D. Y. Palladium-catalyzed remote C−H phosphonylation of indoles at the C4 and C6 positions by a radical approach. Angew. Chem. Int. Ed. 2021, 60, 13871–13876. doi: 10.1002/anie.202103395
8. [8]
  Li, H. T.; Huang, S. H.; Wang, Y. J.; Huo, C. D. Oxidative dehydrogenative [2+3]-cyclization of glycine esters with aziridines leading to imidazolidines. Org. Lett. 2018, 20, 92–95. doi: 10.1021/acs.orglett.7b03448
9. [9]
  Wu, Y. B.; Xie, D.; Zang, Z. L.; Zhou, C. H.; Cai, G. X. Palladium-catalyzed aerobic regio- and stereo-selective olefination reactions of phenols and acrylates via direct dehydrogenative C(sp²)–O cross-coupling. Chem. Commun. 2018, 54, 4437–4440. doi: 10.1039/C8CC01226A
10. [10]
  Rej, S.; Das, A.; Chatani, N. Strategic evolution in transition metal-catalyzed directed C−H bond activation and future directions. Coord. Chem. Rev. 2021, 431, 213683–37. doi: 10.1016/j.ccr.2020.213683
11. [11]
  Li, R.; Xu, X.; Ye, M. Construction of medium rings via transition metal-catalyzed insertion of π-unsaturated compounds into C−H bonds. Chin. J. Org. Chem. 2020, 40, 3196−3202 doi: 10.6023/cjoc202005056
12. [12]
  Carole, W. A.; Colacot, T. J. Understanding palladium acetate from a user perspective. Chem. Eur. J. 2016, 22, 7686−7695. doi: 10.1002/chem.201601450
13. [13]
  Shao, Q.; Wu, K.; Zhuang, Z.; Qian, S.; Yu, J. Q. From Pd(OAc)₂ to chiral catalysts: the discovery and development of bifunctional mono-N-protected amino acid ligands for diverse C−H functionalization reactions. Acc. Chem. Res. 2020, 53, 833−851. doi: 10.1021/acs.accounts.9b00621
14. [14]
  Meng, G.; Lam, N. Y. S.; Lucas, E. L.; Saint-Denis, T. G.; Verma, P.; Chekshin, N.; Yu, J. Q. Achieving site-selectivity for C−H activation processes based on distance and geometry: a carpenter's approach. J. Am. Chem. Soc. 2020, 142, 10571−10591. doi: 10.1021/jacs.0c04074
15. [15]
  Lin, T. Z.; Qian, P. C.; Wang, Y. E.; Ou, M. J.; Jiang, L.; Zhu, C.; Xu, Y. C.; Xiong, D.; Mao, J. Y. Palladium-catalyzed direct arylation of 2-pyridylmethyl silanes with aryl bromides. Org. Lett. 2021, 23, 3000−3003. doi: 10.1021/acs.orglett.1c00677
16. [16]
  Halder, P.; Roy, T.; Das, P. Recent developments in selective N-arylation of azoles. Chem. Commun. 2021, 57, 5235−5249. doi: 10.1039/D1CC01265G
17. [17]
  Thongpaen, J.; Manguin, R.; Baslé, O. Chiral N-heterocyclic carbene ligands enable asymmetric C−H bond functionalization. Angew. Chem. Int. Ed. 2020, 59, 10242–10251. doi: 10.1002/anie.201911898
18. [18]
  Zhang, L.; Fang, D. C. An explicit interpretation of the directing group effect for the Pd(OAc)₂-catalyzed aromatic C–H activations. J. Org. Chem. 2016, 81, 7400−7410. doi: 10.1021/acs.joc.6b00997
19. [19]
  Zhou, J.; Zhou, Y.; Li, Y.; Zhang, J.; Zhang, L. DFT mechanistic study on palladium-catalyzed redox-neutral hydroarylation of unactivated alkenes with arylboronic acids. Asian J. Org. Chem. 2021, 10, 412−420. doi: 10.1002/ajoc.202000647
20. [20]
  Davies, D. L.; Macgregor, S. A.; McMullin, C. L. Computational studies of carboxylate-assisted C–H activation and functionalization at group 8~10 transition metal centers. Chem. Rev. 2017, 117, 8649−8709. doi: 10.1021/acs.chemrev.6b00839
21. [21]
  Ling, B.; Liu, Y.; Jiang, Y. Y.; Liu, P.; Bi, S. Mechanistic insights into the ruthenium-catalyzed [4+1] annulation of benzamides and propargyl alcohols by DFT studies. Organometallics 2019, 38, 1877−1886. doi: 10.1021/acs.organomet.8b00769
22. [22]
  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.; Montgomery, J. A. Jr.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; 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 A. 02, Gaussian, Inc., Wallingford, CT 2009.
23. [23]
  Becke, A. D. Density-functional thermochemistry. Ⅲ. The role of exact exchange. J. Chem. Phys. 1993, 98, 5648–5652. doi: 10.1063/1.464913
24. [24]
  Godbout, N.; Salahub, D. R.; Andzelm, J.; Wimmer, E. Optimization of Gaussian-type basis sets for local spin density functional calculations. Part Ⅰ. Boron through neon, optimization technique and validation. Can. J. Chem. 1992, 70, 560−571. doi: 10.1139/v92-079
25. [25]
  Sosa, C.; Andzelm, J.; Elkin, B. C.; Wimmer, E.; Dobbs, K. D.; Dixon, D. A. A local density functional study of the structure and vibrational frequencies of molecular transition-metal compounds. J. Phys. Chem. 1992, 96, 6630−6636. doi: 10.1021/j100195a022
26. [26]
  Scalmani, G.; Frisch, M. J. Continuous surface charge polarizable continuum models of solvation. I. General formalism. J. Chem. Phys. 2010, 132, 114110−114124. doi: 10.1063/1.3359469
27. [27]
  Grimme, S. Semiempirical GGA-type density functional constructed with a long-range dispersion correction. J. Comput. Chem. 2006, 27, 1787−1799. doi: 10.1002/jcc.20495
28. [28]
  Weigend, F. Accurate Coulomb-fitting basis sets for H to Rn. Phys. Chem. Chem. Phys. 2006, 8, 1057−1065. doi: 10.1039/b515623h
29. [29]
  Zhang, L.; Jiang, B.; Chen, Y.; Lv, J. F.; Feng, W. C. A computational study on the reaction mechanisms of nickel-catalyzed diarylation of alkenes. Eur. J. Org. Chem. 2019, 2019, 6217–6224. doi: 10.1002/ejoc.201900940
30. [30]
  Zhou, Y.; Xue, R. C.; Feng, Y.; Zhang, L. How does HOTf/HFIP cooperative system catalyze the ring-opening reaction of cyclopropanes? A DFT study. Asian J. Org. Chem. 2020, 9, 311–316. doi: 10.1002/ajoc.202000031
31. [31]
  Pearson, R. G. Antisymbiosis and the trans effect. Inorg. Chem. 1973, 12, 712–713. doi: 10.1021/ic50121a052
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