Figure 1
Overview of the historical development of the catalytic C-H activation procedures.
1010 Kosri, C.; Kiatphuengporn, S.; Butburee, T.; Youngjun, S.; Thongratkaew, S.; Faungnawakij, K.; Yimsukanan, C.; Chanlek, N.; Kidkhunthod, P.; Wittayakun, J.; Khemthong, P.; Catal. Today, in press, DOI: 10.1016/j.cattod.2020.04.061.
https://doi.org/10.1016/j.cattod.2020.04...
11 Naikwadi, D. R.; Ravi, K.; Singh, A. S.; Advani, J. H.; Biradar, A. V.; ACS Omega 2020, 5, 14291.-1212 Liu, N.; Qiao, N.; Liu, F.-S.; Wang, S.; Liang, Y.; J. Mol. Struct. 2020, 1218, 128537.,2727 Dimroth, O.; Ber. Dtsch. Chem. Ges. 1902, 35, 2032.,2828 Janowicz, A. H.; Bergman, R. G.; J. Am. Chem. Soc. 1982, 104, 352.
Figure 2
The number of publications covering the topic “C-H activation” (Web of Science, data collected on July 10th, 2020).
Figure 3
Global contribution to the publications covering the topic “C-H activation” from 2019. (Web of Science, data collected on July 10th, 2020).
Scheme 1
Most common proposed mechanism pathways.
Scheme 2
Base-assisted C-H activation proposed mechanism.
Scheme 3
(a) Innate selectivity via steric and electronic properties, (b) guided selectivity and (c) examples of directing groups.
Scheme 4
Example of successful rhodium-catalyzed C-H activation processes using quinones as innate directing-groups.6767 Jardim, G. A. M.; Bower, J. F.; da Silva Júnior, E. N.; Org. Lett. 2016, 18, 4454.
Scheme 5
Examples of bidentate directing groups (BDG).
Scheme 6
Schematic representation of template assistance in remote C-H activation.
Scheme 7
Template DG designed to selective C-H alkenylation of benzylic alcohol derivatives, followed by DG removal reported by Yu and co-workers.6969 Leow, D.; Li, G.; Mei, T. S.; Yu, J. Q.; Nature 2012, 486, 518.
Scheme 8
Distal para-C-H activation of arenes assisted by biphenyl template-based assembly reported by Maiti and co-workers.7070 Bag, S.; Patra, T.; Modak, A.; Deb, A.; Maity, S.; Dutta, U.; Dey, A.; Kancherla, R.; Maji, A.; Hazra, A.; Bera, M.; Maiti, D.; J. Am. Chem. Soc. 2015, 137, 11888.
Scheme 9
Examples of template for distal meta- and para-selective C-H activation.
Scheme 10
Isomeric effect of substituents on the substrate (starting materials).
Scheme 11
Example of the isomeric effect of substituents reported by Ackermann and co-workers5353 Ma, W.; Mei, R.; Tenti, G.; Ackermann, L.; Chem.-Eur. J. 2014, 20, 15248. and Dixneuf and co-workers.5858 Arockiam, P. B.; Fischmeister, C.; Bruneau, C.; Dixneuf, P. H.; Green Chem. 2011, 13, 3075.
Scheme 12
Some examples of C-H activation using 2-phenylpyridine (64) with the insertion of different functional groups.7979 Das, P.; Saha, D.; Guin, J.; ACS Catal. 2016, 6, 6050.
80 Perumgani, P. C.; Parvathaneni, S. P.; Babu, G. V. S.; Srinivas, K.; Mandapati, M. R.; Catal. Lett. 2018, 148, 1067.
81 Li, J.; Ackermann, L.; Angew. Chem., Int. Ed. 2015, 54, 3635.
82 Zhang, H.; Yang, Z.; Liu, J.; Yu, X.; Wang, Q.; Wu, Y.; Org. Chem. Front. 2019, 6, 967.
83 Wan, T.; Du, S.; Pi, C.; Wang, Y.; Li, R.; Wu, Y.; Cui, X.; ChemCatChem 2019, 11, 3791.-8484 Su, L.; Guo, D.-D.; Li, B.; Guo, S.-H.; Pan, G.-F.; Gao, Y.-R.; Wang, Y.-Q.; ChemCatChem 2017, 9, 2001.
Scheme 13
Cobalt-catalyzed C-H alkenylation.103103 Zhou, X.; Luo, Y.; Kong, L.; Xu, Y.; Zheng, G.; Lan, Y.; Li, X.; ACS. Catal. 2017, 7, 7296.
Figure 4
Comparison of the usual visual profile seen between a TLC and a column chromatography (CC) template.
Figure 5
Procedure to perform a bidimensional TLC.
Figure 6
Correlation between the thickness of the column vs. dry-loading amount and spot separation vs. the height of silica.
Scheme 14
Example of palladium-catalyzed meta-selective alkenylation.116116 Lee, S.; Lee, H.; Tan, K. L.; J. Am. Chem. Soc. 2013, 135, 18778.
Scheme 15
Ruthenium-catalyzed double C-H annulation.117117 Silva Júnior, E. N.; Carvalho, R. L.; Almeida, R. G.; Rosa, L. G.; Fantuzzi, F.; Rogge, T.; Costa, P. M. S.; Pessoa, C.; Jacob, C.; Ackermann, L.; Chem.-Eur. J. 2020, 26, 10981. *An additional 5 mol% of the catalyst was added after 12 h.
Figure 7
Examples of common palladium, rhodium, iridium and ruthenium catalysts.
Scheme 16
Examples of C–H activation using a less expensive catalyst.137137 Ding, Z.; Yoshikai, N.; Angew. Chem., Int. Ed. 2012, 51, 4698.
138 Ruan, Z.; Sauermann, N.; Manoni, E.; Ackermann, L.; Angew. Chem., Int. Ed. 2017, 56, 3172.
139 Kimura, N.; Kochi, T.; Kakiuchi, F.; J. Am. Chem. Soc. 2017, 139, 14849.
140 Chen, X.; Hao, X.-S.; Goodhue, C. E.; Yu, J.-Q.; J. Am. Chem. Soc. 2006, 128, 6790.-141141 Yoshida, Y.; Kurahashi, T.; Matsubara, S.; Chem. Lett. 2011, 40, 1140.
Scheme 17
Solvent effect on C-H activation of 2-pyridones reported by Miura and co-workers.142142 Hazra, S.; Hirano, K.; Miura, M.; Asian J. Org. Chem. 2019, 8, 1097.
Scheme 18
Examples of the influence of additives on the reaction.150150 Sherikar, M. S.; Kapanaiah, R.; Lanke, V.; Prabhu, K. R.; Chem. Commun. 2018, 54, 11200.,151151 Lai, R.; Wu, X.; Lv, S.; Zhang, C.; He, M.; Chen, Y.; Wang, Q.; Hai, L.; Wu, Y.; Chem. Commun. 2019, 55, 4039.
Figure 8
Easy processes to optimize the use of a heating plate.
Scheme 19
Clarification of the calculation of yield, conversion and recovering percentages.
Figure 9
Chemical shift (d) of the hydrogen atoms of the compounds 1,4-dinitrobenzene (99) and 1,3,5-trimethoxybenzene (100).
Figure 10
Flowchart to calculate yield in situ using 1H NMR analysis (see text). mIS: mass of internal standard; areaPR: obtained area of the signal of the product; HIS: number of hydrogen atoms related to the signal of the internal standard (in the case of 1,4-dinitrobenzene, HIS = 4); MWSM: molecular weight of the starting material; nSM: molar equivalence of the starting material from the balanced equation; MWIS: molecular weight of the internal standard (in the case of 1,4-dinitrobenzene, MWIS = 168.1); HPR: number of hydrogen atoms related to the signal of the product; mSM: applied mass of starting material; nPR: molar equivalence of the product from the balanced equation.
Figure 11
Flowchart to build the calibration curve (see text for further information).
Figure 12
Example of a linear graph between the concentration of product and ratio of areas of chromatogram peaks.
Figure 13
Flowchart to calculate yield in situ using GC-MS analysis. Conc.: concentration of product obtained from the linear equation; VR: volume of solvent applied in the reaction; MWSM: molecular weight of the starting material; nSM: molar equivalence of the starting material from the balanced equation; mSM: applied mass of starting material; nPR: molar equivalence of the product from the balanced equation.
Scheme 20
Scope variations on the C-H activation reported by der Eycken and co-workers.172172 Xu, J.; Sharma, N.; Sharma, U. K.; Li, Z.; Song, G.; der Eycken, E. V. V.; Adv. Synth. Catal. 2015, 357, 2615.
Scheme 21
Late-stage example using a steroid-based substrate.138138 Ruan, Z.; Sauermann, N.; Manoni, E.; Ackermann, L.; Angew. Chem., Int. Ed. 2017, 56, 3172.
Scheme 22
Comparison of small-scale and large-scale C-H activations.190190 Ding, Q.; Ye, S.; Cheng, G.; Wang, P.; Farmer, M. E.; Yu, J.-Q.; J. Am. Chem. Soc. 2017, 139, 417. aNormal-scale reaction: 0.1 mmol of substrate; bscaled-up reaction: 3.0 mmol of substrate.
Scheme 23
Sequential ruthenium catalyzed C-H arylation and its proposed mechanism.196196 Li, B.; Bheeter, C. B.; Darcel, C.; Dixneuf, P. H.; Top. Catal. 2014, 57, 833.
Scheme 24
Palladium-catalyzed C-H arylation of a free primary amine203203 Xu, Y.; Young, M. C.; Wang, C.; Magness, D. M.; Dong, G.; Angew. Chem., Int. Ed. 2016, 55, 9084. and its mechanistic studies by computational analysis.201201 Hu, X.-X.; Liu, J.-B.; Wang, L.-L.; Huang, F.; Sun, C.-Z.; Chen, D.-Z.; Org. Chem. Front. 2018, 5, 1670.
Scheme 25
Cobalt-catalyzed C-H activation and its respective mechanistic studies.193193 Baccalini, A.; Vergura, S.; Dolui, P.; Maiti, S.; Dutta, S.; Maity, S.; Khan, F. F.; Lahiri, G. K.; Zanoni, G.; Maiti, D.; Org. Lett. 2019, 21, 8842.
Scheme 26
Palladium-catalyzed Negishi cross-coupling reaction and electrospray ionization-mass spectrometry (ESI-MS) mechanistic studies.214214 Yan, X.; Sokol, E.; Li, X.; Li, G.; Xu, S.; Cooks, R. G.; Angew. Chem., Int. Ed. 2014, 53, 5931.
Scheme 27
Ruthenium-catalyzed C-H oxygenation220220 Dias, G. G.; Rogge, T.; Kuniyil, R.; Jacob, C.; Menna-Barreto, R. F. S.; da Silva Júnior, E. N.; Ackermann, L.; Chem. Commun. 2018, 54, 12840. and alkenylation227227 Dias, G. G.; do Nascimento, T. A.; de Almeida, A. K. A.; Bombaça, A. C. S.; Menna-Barreto, R. F. S.; Jacob, C.; Warratz, S.; da Silva Júnior, E. N.; Ackermann, L.; Eur. J. Org. Chem. 2019, 2019, 2344. of quinones and IC50/24 h against the T. cruzi.
Scheme 28
Example of derivatization after a C–H activation reaction.228228 Yoo, E. J.; Wasa, M.; Yu, J.-Q.; J. Am. Chem. Soc. 2010, 132, 17378.
Scheme 29
Rhodium-catalyzed C–H iodination and its respective derivatization.232232 Jardim, G. A. M.; da Silva Júnior, E. N.; Bower, J. F.; Chem. Sci. 2016, 7, 3780.,233233 Jardim, G. A. M.; Oliveira, W. X. C.; Freitas, R. P.; Menna-Barreto, R. F. S.; Silva, T. L.; Goulart, M. O. F.; da Silva Júnior, E. N.; Org. Biomol. Chem. 2018, 16, 1686. *[RhCp*Cl2]2 (5.0 mol%), AgNTf2 (27.0 mol%).