Cobalt-Catalyzed α-Arylation of 1-Trimethylsilyl-2-aryl Acetylene

doi:10.6023/cjoc202603046

Abstract

A synergistic catalytic, chemo-, regio- and stereoselective arylation reaction of 1-trimethylsilyl-2-arylacetylene using cobalt diacetylacetonate and diphenylphosphine methane has been developed, effectively synthesizing 1,2-diaryl- vinylsilyl compounds with multiple functional groups. This method has the advantages of good functional group tolerance, moderate to good yield, easy preparation on a gram scale, and the presence of vinyl silicon structural units in the product can achieve multiple synthetic transformations. At the same time, this work also developed new synthetic applications of 3,4-dihydro-1(2H)-isoquinolinone compounds.

Key words: cobalt-catalyzed, alkynes, chemselectivity, regioselectivity, stereoselectivity, arylation

Cite this article

Liping Chen, Rui Ma, Jianjun Chi, Yufan Jin, Qing Wang, Yang Wang, Xuehua Zhu, Yubo Pang. Cobalt-Catalyzed α-Arylation of 1-Trimethylsilyl-2-aryl Acetylene[J]. Chinese Journal of Organic Chemistry, 2026, 46(7): 2760-2769.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 6

References 16

[1]	(a) Corpas, J.; Mauleón, P.; Arrayás, R.; Carretero, J. C. ACS Catal. 2021, 11, 7513. doi: 10.1021/acscatal.1c01421
	(b) Teng, S.; Liang, P.; Zhou, J. S. Chem. Soc. Rev. 2025, 54, 2664. doi: 10.1039/D4CS01130A
	(c) Sun, L.-L.; Sun, K. Chin. J. Org. Chem. 2025, 45, 3655 (in Chinese). doi: 10.6023/cjoc202502004
	(孙良龙, 孙凯, 有机化学, 2025, 45, 3655.)
[2]	For selected recent examples on merger of transition metal catalysis with alkynes, see: (a) Jin, Y.; Meng, R.; Wu, C.; Zhang, X.; Xing, J.; Dou, X. Org. Lett. 2025, 27, 12142. doi: 10.1021/acs.orglett.5c03958
	(b) Chen, K.; Zhu, H.; Jiang, S.; Ding, K.; Peng, Q.; Wang, X.; Nat. Commun. 2025, 16, 3077. doi: 10.1038/s41467-025-58398-x
	(c) Chen, S.; Wang, Y.-N.; Xie, J.; Li, W.; Ye, M.; Ma, X.; Yang, K.; Li, S.; Lan, Y.; Song, Q. Nat. Commun. 2024, 15, 5479. doi: 10.1038/s41467-024-49870-1
	(d) Li, H.; Tian, X.; Dang, Q.-Q.; Zhang, J.; Wen, Z.-K. ACS Catal. 2024, 14, 9985. doi: 10.1021/acscatal.4c01944
	(e) Chang, S.; Guo, C.; Zhong, R.-M.; Lai, Y.-L.; Guo, H.; Huang, L.-B. Org. Lett. 2024, 26, 3733. doi: 10.1021/acs.orglett.4c00747
	(f) Basha, K. S.; Balamurugan, R. Org. Lett. 2023, 25, 4803. doi: 10.1021/acs.orglett.3c01492
	(g) Sun, Q.; Sun, Z.-Y.; Yu, Z.; Wang, G.-W. Chin. J. Org. Chem. 2022, 42, 2515 (in Chinese). doi: 10.6023/cjoc202203054
	(孙奇, 孙泽颖, 俞泽, 王光伟, 有机化学, 2022, 42, 2515.) doi: 10.6023/cjoc202203054
	(h) Tang, J.-B.; Bian, J.-Q.; Zhang, Y.-S.; Cheng, Y.-F.; Wen, H.-T.; Yu, Z.-L.; Li, Z.-L.; Gu, Q.-S.; Chen, G.-Q.; Liu, X.-Y. Org. Lett. 2022, 24, 2536. doi: 10.1021/acs.orglett.2c00692
[3]	For selected recent examples of steric hindrance effects controlling the regioselectivity of alkynes, see: (a) Zhou, Q.; Meng, R.; Xing, J.; Yao, W.; Dou, X. ACS Catal. 2023, 13, 8516. doi: 10.1021/acscatal.3c01856 pmid: 11772106
	(b) Hayashi, T.; Inoue, K.; Taniguchi, N.; Ogasawara, M. J. Am. Chem. Soc. 2001, 123, 9918. pmid: 11772106
	(c) Lautens, M.; Yoshida, M. Org. Lett. 2002, 4, 123. pmid: 11772106
	(d) Xu, X.; Chen, J.; Gao, W.; Wu, H.; Ding, J.; Su, W. Tetrahedron 2010, 66, 2433. doi: 10.1016/j.tet.2010.01.086 pmid: 11772106
	(e) Kim, N.; Kim, K. S.; Gupta, A. K.; Oh, C. H. Chem. Commun. 2004, 618. pmid: 11772106
[4]	For selected reviews and examples of alkenylsilicon conversion, see: (a) Komiyama, T.; Minami, Y.; Hiyama, T. ACS Catal. 2017, 7, 631. doi: 10.1021/acscatal.6b02374 pmid: 41001625
	(b) Korch, K. M.; Watson, D. A. Chem. Rev. 2019, 119, 8192. doi: 10.1021/acs.chemrev.8b00628 pmid: 41001625
	(c) Ye, F.; Xu, Z.; Xu, L.-W. Acc. Chem. Res. 2021, 54, 452. doi: 10.1021/acs.accounts.0c00740 pmid: 41001625
	(d) Yin, K.; Zhang, J.; Pan, D.; Chen, S.-H.; Chen, S.; Shi, Y.; Huang, G.; Zhao, D. Nat. Commun. 2025, 16, 797. doi: 10.1038/s41467-025-56232-y pmid: 41001625
	(e) Zhang, Z.; Li, L.; Xu, H.; Lee, C.-L. K.; Jia, Z.; Loh, T.-P. J. Am. Chem. Soc. 2024, 146, 1776. doi: 10.1021/jacs.3c12050 pmid: 41001625
	(f) Nagashima, Y.; Suzuki, M.; Shimose, A.; Arai, R.; Tanaka, K.; Uchiyama, M. JACS Au 2025, 5, 4481. doi: 10.1021/jacsau.5c00831 pmid: 41001625
	(g) Tan, Y.; Ying, J.; Yu, B.; Lu, Z. Chin. J. Org. Chem. 2023, 43, 3614 (in Chinese). doi: 10.6023/cjoc202306025 pmid: 41001625
	(谭燕, 应佳乐, 於兵, 陆展, 有机化学, 2023, 43, 3614.) pmid: 41001625
[5]	Genin, E.; Michelet, V.; Genêt, J.-P. J. Organomet. Chem. 2004, 689, 3820. doi: 10.1016/j.jorganchem.2004.07.025
[6]	Kong, W.; Che, C.; Wu, J.; Ma, L.; Zhu, G.G. J. Org. Chem. 2014, 79, 5799. doi: 10.1021/jo500925p pmid: 24901791
[7]	Lin, P.-S.; Jeganmohan, M.; Cheng, C.-H. Chem.-Eur. J. 2008, 14, 11296. doi: 10.1002/chem.v14:36
[8]	For selected recent examples of cobalt-catalyzed hydrosilylation of alkynes, see: (a) Guo, J.; Shen, X.; Lu, Z. Angew. Chem. Int. Ed. 2017, 56, 615. doi: 10.1002/anie.v56.2 pmid: 28537588
	(b) Cheng, Z.; Xing, S.; Guo, J.; Cheng, B.; Hu, L.-F.; Zhang, X.-H.; Lu, Z. Chin. J. Chem. 2019, 37, 457. doi: 10.1002/cjoc.v37.5 pmid: 28537588
	(c) Wen, H.; Wan, X.; Huang, Z. Angew. Chem. Int. Ed. 2018, 57, 6319. doi: 10.1002/anie.v57.21 pmid: 28537588
	(d) Docherty, J. H.; Peng, J.; Dominey, A. P.; Thomas, S. P. Nat. Chem. 2017, 9, 595. doi: 10.1038/nchem.2697 pmid: 28537588
	(e) Blasius, C. K.; Vasilenko, V.; Matveeva, R.; Wadepohl, H.; Gade, L. H. Angew. Chem. Int. Ed. 2020, 59, 23010. doi: 10.1002/anie.v59.51 pmid: 28537588
	(f) Chen, J.; Shen, X.; Lu, Z. Angew. Chem. Int. Ed. 2021, 60, 690. doi: 10.1002/anie.v60.2 pmid: 28537588
	(g) Li, Z.; Ying, J.; Lu, Z. Chin. J. Chem. 2025, 44, 553. doi: 10.1002/cjoc.v44.4 pmid: 28537588
	(h) You, Y.; Ge, S. Angew. Chem. Int. Ed. 2021, 60, 20684. doi: 10.1002/anie.v60.38 pmid: 28537588
	(i) Lu, W.; Zhao, Y.; Meng, F. J. Am. Chem. Soc. 2022, 144, 5233. doi: 10.1021/jacs.2c00288 pmid: 28537588
	(j) Cheng, Z.; Li, M.; Zhang, X.-Y.; Sun, Y.; Yu, Q.-L.; Zhang, X.-H.; Lu, Z. Angew. Chem. Int. Ed. 2023, 62, e202215029. doi: 10.1002/anie.v62.1 pmid: 28537588
	(k) Jin, S.; Liu, K.; Wang, S.; Song, Q. J. Am. Chem. Soc. 2021, 143, 13124. doi: 10.1021/jacs.1c04248 pmid: 28537588
[9]	For selected recent examples of cobalt-catalyzed hydroborylation of alkynes, see: (a) Guo, J.; Cheng, B.; Shen, X.; Lu, Z. J. Am. Chem. Soc. 2017, 139, 15316. doi: 10.1021/jacs.7b09832 pmid: 25884604
	(b) Sang, H. L.; Wu, C.; Phua, G. G. D.; Ge, S. ACS Catal. 2019, 9, 10109. doi: 10.1021/acscatal.9b03139 pmid: 25884604
	(c) Li, Z.; Zhao, J.; Xue, W.; Tang, J.; Li, S.; Ge, Y.; Xu, J.; Zheng, X.; Li, R.; Chen, H.; Fu, H. Org. Biomol. Chem. 2024, 22, 4455. doi: 10.1039/D4OB00435C pmid: 25884604
	(d) Doll, J. S.; Heldner, M. L.; Scherr, M.; Ballmann, J.; Roşca, D.-A. ACS Catal. 2023, 13, 8770. doi: 10.1021/acscatal.3c01854 pmid: 25884604
	(e) Sun, Y.; Guan, R.; Liu, Z.; Wang, Y. Chin. J. Org. Chem. 2020, 40, 899 (in Chinese). doi: 10.6023/cjoc201909035 pmid: 25884604
	(孙越, 关瑞, 刘兆洪, 王也铭, 有机化学, 2020, 40, 899.) doi: 10.6023/cjoc201909035 pmid: 25884604
	(f) Zhang, G. Chem. Commun. 2022, 58, 8109. doi: 10.1039/D2CC02815H pmid: 25884604
	(g) González, M. J.; Bauer, F.; Breit, B. Org. Lett. 2021, 23, 8199. doi: 10.1021/acs.orglett.1c02854 pmid: 25884604
	(h) Wen, J.; Huang, Y.; Zhang, Y.; Grützmacher, H.; Hu, P. Nat. Commun. 2024, 15, 2208. doi: 10.1038/s41467-024-46550-y pmid: 25884604
	(i) Obligacion, J. V.; Neely, J. M.; Yazdani, A. N.; Pappas, I.; Chirik, P. J. J. Am. Chem. Soc. 2015, 137, 5855. doi: 10.1021/jacs.5b00936 pmid: 25884604
	(j) Zhang, Y.-D.; Li, X.-Y.; Mo, Q.-K.; Shi, W.-B.; Zhao, J.-B.; Zhu, S.-F. Angew. Chem. Int. Ed. 2022, 61, e202208473. doi: 10.1002/anie.v61.36 pmid: 25884604
	(k) Wu, C.; Ge, S. Chem. Sci. 2020, 11, 2783. doi: 10.1039/C9SC06136C pmid: 25884604
[10]	For selected recent examples of cobalt-catalyzed reductive coupling of alkynes and alkenes, see: (a) Gandeepan, P.; Cheng, C.-H.. Acc. Chem. Res. 2015, 48, 1194. doi: 10.1021/ar500463r
	(b) Gao, S.; Liu, C.; Yang, J.; Zhang, J. Chin. J. Org. Chem. 2023, 43, 1559 (in Chinese). doi: 10.6023/cjoc202209036
	(高师泉, 刘闯军, 杨俊锋, 张俊良, 有机化学, 2023, 43, 1559.) doi: 10.6023/cjoc202209036
	(c) Li, Y.-L.; Zhang, S.-Q.; Chen, J.; Xia, J.-B. J. Am. Chem. Soc. 2021, 143, 7306. doi: 10.1021/jacs.1c03527
	(d) Whyte, A.; Bajohr, J.; Torelli, A.; Lautens, M. Angew. Chem. Int. Ed. 2020, 59, 16409. doi: 10.1002/anie.v59.38
	(e) Zhang, J.-W.; Wu, M; Zhang, Z.-H.; Chong, Q.-L.; Meng, F.-K. Nat. Commun. 2025, 16, 5995. doi: 10.1038/s41467-025-61019-2
	(f) Meng, H.; Xia, Y.-L.; Yu, Q.; Li, Y.-L.; Shu, W. J. Am. Chem. Soc. 2025, 147, 41738. doi: 10.1021/jacs.5c13795
	(g) Guo, N.-X.; Gu, Z.-Y.; Zhu, M.-W.; Chen, C.; Xia, J.-B. Angew. Chem. Int. Ed. 2025, 64, e202512923. doi: 10.1002/anie.v64.43
[11]	For selected recent examples of cobalt-catalyzed other functionalization of alkynes and C(sp²)—C(sp²) bond construction, see: (a) Ying, J.; Tan, Y.; Lu, Z. Nat. Commun. 2024, 15, 8057. doi: 10.1038/s41467-024-52249-x pmid: 36920031
	(b) Sun, Y.; Wang, B.; Wang, C.; Li, J.; Chen, J.; Hong, X.; Lu, Z. Sci. Chin. Chem. 2024, 68, 2491. doi: 10.1007/s11426-024-2362-4 pmid: 36920031
	(c) Wang, T.; Guan, J.-X.; Tan, Y.-X.; Tian, P. Org. Lett. 2023, 25, 5935. doi: 10.1021/acs.orglett.3c01958 pmid: 36920031
	(d) Luo, M.; Liu, Z.; Chen, H.; Fu, H.; Li, R.; Zheng, X. J. Catal. 2024, 433, 115459. doi: 10.1016/j.jcat.2024.115459 pmid: 36920031
	(e) Chen, J.; Ying, J.; Lu, Z. Nat. Commun. 2022, 13, 4518. doi: 10.1038/s41467-022-32291-3 pmid: 36920031
	(f) Chen, L.; Yang, J.; Li, L.; Weng, Z.; Kang, Q. Tetrahedron Lett. 2014, 55, 6096. doi: 10.1016/j.tetlet.2014.09.042 pmid: 36920031
	(g) Li, Y.; Liu, D.; Wan, L.; Zhang, J.-Y.; Lu, X.; Fu, Y. J. Am. Chem. Soc. 2022, 144, 13961. doi: 10.1021/jacs.2c06279 pmid: 36920031
	(h) Jiang, H.; He, X.-K.; Jiang, X.; Zhao, W.; Lu, L.-Q.; Cheng, Y.; Xiao, W.-J. J. Am. Chem. Soc. 2023, 145, 6944. doi: 10.1021/jacs.3c00462 pmid: 36920031
	(i) Staronova, L.; Yamazaki, K.; Xu, X.; Shi, H.; Bickelhaupt, F. M.; Hamlin, T. A.; Dixon, D. J. Angew. Chem. Int. Ed. 2024, 63, e202316021. doi: 10.1002/anie.v63.13 pmid: 36920031
	(j) Wang, B.-J.; Jiang, T.-Y.; Jiang, Y.-L.; Wu, X.; Yao, Q.-J.; Shi, B.-F. J. Am. Chem. Soc. 2025, 147, 45785. doi: 10.1021/jacs.5c18900 pmid: 36920031
	(k) Si, X.-J.; Yang, D.; Sun, M.-C.; Wei, D.; Song, M.-P.; Niu, J.-L. Nat. Synth. 2022, 1, 709. doi: 10.1038/s44160-022-00114-4 pmid: 36920031
	(l) Yu, J.-X.; Cheng, Y.-Y.; Chen, B.; Tung, C.-H.; Wu, L.-Z. Angew. Chem. Int. Ed. 2022, 61, e202209293. doi: 10.1002/anie.v61.40 pmid: 36920031
	(m) Guo, J.-D.; Chen, Y.-J.; Wang, C.-H.; He, Q.; Yang, X.-L.; Ding, T.-Y.; Zhang, K.; Ci, R.-N.; Chen, B.; Tung, C.-H.; Wu, L.-Z. Angew. Chem. Int. Ed. 2023, 62, e202214944. doi: 10.1002/anie.v62.7 pmid: 36920031
	(n) Qian, G.-F.; Chen, R.-B.; Miao, T.-T.; Xiao, Y.; Li, S.; Gao, W.-H.; Zhong, J.-J. Org. Lett. 2025, 27, 7188. doi: 10.1021/acs.orglett.5c02125 pmid: 36920031
[12]	(a) Ueda, M.; Ueno, T.; Suyama, Y.; Ryu, I. Chem. Commun. 2016, 52, 13237. doi: 10.1039/C6CC08032D
	(b) Ueda, M.; Ueno, T.; Suyama, Y.; Ryu, I. Tetrahedron Lett. 2017, 58, 2972. doi: 10.1016/j.tetlet.2017.06.049
[13]	Tang, L.; Liu, X.; Wang, X.; Liu, X.; Huang, X.; Ni, Q.; He, C.; Luo, G.; Ma, Y. ACS Catal. 2025, 15, 1596. doi: 10.1021/acscatal.4c07667
[14]	Cox, P. A.; Leach, A. G.; Campbell, A. D.; Jones, G. C.; J. Am. Chem. Soc. 2016, 138, 9145. doi: 10.1021/jacs.6b03283
[15]	(a) Andreetta, P.; Martin, R. T.; Souilah, C.; Rentería-Gómez, Á.; Song, Z.; Bayat, Y. K.; Ivlev, S.; Gutierrez, O.; Casitas, A. Angew. Chem. Int. Ed. 2023, 62, e202310129. doi: 10.1002/anie.v62.46
	(b) Wei, H.; Luo, Y.; Ren, J.; Yuan, Q.; Zhang, W. Nat. Commun. 2024, 15, 8775. doi: 10.1038/s41467-024-53005-x
[16]	Maloney, T. P.; Berman, J. L.; Michael, F. E. Angew. Chem. Int. Ed. 2022, 61, e202210109. doi: 10.1002/anie.v61.45

Entry	Ligand (equiv.)	Solvent	Temp./℃	Yeild^b/% (3aa/4aa)	Z/E ratio (3aa)
1	dppe (0.1)	MeCN	80	5	>20/1
2	dppe (0.1)	MeCN	100	56 (1/1)	>20/1
3	dppe (0.1)	MeCN	120	58 (1/1)	>20/1
4	dppe (0.1)	THF	100
5	dppe (0.1)	IPAc	100
6	dppe (0.1)	DMA	100	Trace
7	dppe (0.1)	Toluene	100
8	dppe (0.1)	EtOH	100
9	dppp (0.1)	MeCN	100	50 (1/1.5)	>20/1
10	dppb (0.1)	MeCN	100	37 (1/2)	>20/1
11	dppm (0.1)	MeCN	100	63	>20/1
12	dppm (0.2)	MeCN	100	78	>20/1

Entry	Ligand (equiv.)	Solvent	Temp./℃	Yeild^b/% (3aa/4aa)	Z/E ratio (3aa)
1	dppe (0.1)	MeCN	80	5	>20/1
2	dppe (0.1)	MeCN	100	56 (1/1)	>20/1
3	dppe (0.1)	MeCN	120	58 (1/1)	>20/1
4	dppe (0.1)	THF	100
5	dppe (0.1)	IPAc	100
6	dppe (0.1)	DMA	100	Trace
7	dppe (0.1)	Toluene	100
8	dppe (0.1)	EtOH	100
9	dppp (0.1)	MeCN	100	50 (1/1.5)	>20/1
10	dppb (0.1)	MeCN	100	37 (1/2)	>20/1
11	dppm (0.1)	MeCN	100	63	>20/1
12	dppm (0.2)	MeCN	100	78	>20/1

钴催化1-三甲硅基-2-芳基乙炔的α位芳基化反应