Rhodium(III)-Catalyzed Enantioselective Allylic C—H Alkylation of Unactivated Alkenes with α‑Diazocarbonyl Compounds

doi:10.6023/cjoc202505004

Chinese Journal of Organic Chemistry ›› 2025, Vol. 45 ›› Issue (6): 2109-2120.DOI: 10.6023/cjoc202505004 Previous Articles Next Articles

ARTICLES

铑(III)催化的非活化烯烃与α-重氮羰基化合物的对映选择性烯丙位C—H键烷基化反应

周强, 杨宝臻^c^,^d, 郝贵林, 罗木鹏^c, 曹石^c, 赵蓓^d^,^*(), 袁华^a^,^b^,^*(), 王守国^c^,^*()

^a 湖南科技大学化学化工学院湖南湘潭 411201
^b 湖南科技大学理论有机化学与功能分子教育部重点实验室湖南湘潭 411201
^c 深圳大学化学与环境工程学院广东深圳 518060
^d 苏州大学材料与化学化工学部江苏苏州 215123

收稿日期:2025-05-06 修回日期:2025-05-17 发布日期:2025-05-20
通讯作者: 赵蓓, 袁华, 王守国
基金资助:
广东省自然科学基金(2024A1515011368); 深圳市科学技术创新委员会基金(JCYJ20220818101601004); 深圳市科学技术创新委员会基金(JCYJ20220818095801004)

Rhodium(III)-Catalyzed Enantioselective Allylic C—H Alkylation of Unactivated Alkenes with α‑Diazocarbonyl Compounds

Qiang Zhou, Baozhen Yang^c^,^d, Guilin Hao, Mupeng Luo^c, Shi Cao^c, Bei Zhao^d^,^*(), Hua Yuan^a^,^b^,^*(), Shouguo Wang^c^,^*()

^a School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan, Hunan 411201
^b Key Laboratory of Theoretical Organic Chemistry and Function Molecule of Ministry of Education, Xiangtan, Hunan 411201
^c College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen, Guangdong 518060
^d College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, Jiangsu 215123

Received:2025-05-06 Revised:2025-05-17 Published:2025-05-20
Contact: Bei Zhao, Hua Yuan, Shouguo Wang
Supported by:
Guangdong Basic and Applied Basic Research Foundation(2024A1515011368); Science, Technology and Innovation Commission of Shenzhen Municipality(JCYJ20220818101601004); Science, Technology and Innovation Commission of Shenzhen Municipality(JCYJ20220818095801004)

1. .pdf(8808KB)

Abstract

Direct enantioselective allylic C—H functionalization has emerged as a powerful strategy for the asymmetric synthesis of highly valuable chiral products. Herein, a Rh(III)-catalyzed enantioselective allylic C—H alkylation of unactivated alkenes with α-diazo carbonyl compounds is described, enabling direct access to chiral products with high efficiency (up to 77% yield, 92% ee, and >10∶1 B/L (branched/linear) selectivity). This atom-and step-economical protocol directly converts simple, unactivated substrates into valuable enantioenriched products under mild conditions, providing an efficient catalytic system for asymmetric allylic C—H functionalization.

Key words: C—H bond activation, asymmetric allylic alkylation, Rh(Ⅲ)-catalysis, diazo compound

Cite this article

Qiang Zhou, Baozhen Yang, Guilin Hao, Mupeng Luo, Shi Cao, Bei Zhao, Hua Yuan, Shouguo Wang. Rhodium(III)-Catalyzed Enantioselective Allylic C—H Alkylation of Unactivated Alkenes with α‑Diazocarbonyl Compounds[J]. Chinese Journal of Organic Chemistry, 2025, 45(6): 2109-2120.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 7

References 13

[1]	(a) Trost, B. M.; Van Vranken, D. L. Chem. Rev. 1996, 96, 395.
	(b) Cheng, Q.; Tu, H.-F.; Zheng, C.; Qu, J.-P.; Helmchen, G.; You, S.-L. Chem. Rev. 2019, 119, 1855.
	(c) Trost, B. M.; Crawley, M. L. Chem. Rev. 2003, 103, 2921.
	(d) Harutyunyan, S. R.; den Hartog, T.; Geurts, K.; Minnaard, A. J.; Feringa, B. L. Chem. Rev. 2008, 108, 2824.
	(e) Butt, N. A.; Zhang, W. Chem. Soc. Rev. 2015, 44, 7929.
[2]	(a) Süsse, L.; Stoltz, B. M. Chem. Rev. 2021, 121, 4084.
	(b) Kalita, S. J.; Huang, Y.-Y.; Schneider, U. Sci. Bull. 2020, 65, 1865.
	(c) Sempere, Y.; Alfke, J. L.; Rössler, S. L.; Carreira, E. M. Angew. Chem. Int. Ed. 2019, 58, 9537.
	(d) Chang, X.; Che, C.; Wang, Z.-F.; Wang, C.-J. CCS Chem. 2022, 4, 1414.
	(e) Huo, X.; Zhao, L.; Luo, Y.; Wu, Y.; Sun, Y.; Li, G.; Gridneva, T.; Zhang, J.; Ye, Y.; Zhang, W. CCS Chem. 2022, 4, 1720.
	(f) Pal, D.; Veeranna, K. D.; Wong, Y. F.; Evans, P. A. Sci. China Chem. 2024, 67, 3791.
	(g) Jiang, R.; Zhao, Q.-R.; Zheng, C.; You, S.-L. Nat. Catal. 2022, 5, 1089.
	(h) Wang, T.-C.; Fan, L.-F.; Shen, Y.; Wang, P.-S.; Gong, L.-Z. J. Am. Chem. Soc. 2019, 141, 10616.
	(i) Fan, L.-F.; Luo, S.-W.; Chen, S.-S.; Wang, T.-C.; Wang, P.-S.; Gong, L. Z. Angew. Chem. Int. Ed. 2019, 58, 16806.
	(j) Stanley, L. M.; Bai, C.; Ueda, M.; Hartwig, J. F. J. Am. Chem. Soc. 2010, 132, 8918.
	(k) Richard, F.; Clark, P.; Hannam, A.; Keenan, T.; Jean, A.; Arseniyadis, S. Chem. Soc. Rev. 2024, 53, 1936.
	(l) Bartels, B.; García‐Yebra, C.; Rominger, F.; Helmchen, G. Eur. J. Inorg. Chem. 2002, 2569.
[3]	(a) Janssen, J. P.; Helmchen, G;. Tetrahedron Lett. 1997, 38, 8025.
	(b) Alonso, D. A.; Maciá, B.; Pastor, I. M.; Baeza, A. ACS Org. Inorg. Au 2024, 4, 269.
	(c) Bartels, B.; Helmchen, G. Chem. Commun. 1999, 741.
	(d) Moghadam, F. A.; Hicks, E. F.; Sercel, Z. P.; Cusumano, A. Q.; Bartberger, M. D.; Stoltz, B. M. J. Am. Chem. Soc. 2022, 144, 7983.
	(e) Hayashi, T.; Okada, A.; Suzuka, T.; Kawatsura, M. Org. Lett. 2003, 5, 1713.
[4]	(a) Trost, B. M.; Fandrick, D. R.; Dinh, D. C. J. Am. Chem. Soc. 2005, 127, 14186.
	(b) Koschker, P.; Breit, B. Acc. Chem. Res. 2016, 49, 1524.
	(c) Wang, W.; Hu, Y.; Li, K.; Xu, J.; Zhang, C.; Zhou, L.; Zhu, L.; Guo, H. ACS Catal. 2024, 14, 9940.
[5]	Sempere, Y.; Carreira, E. M. Angew. Chem. Int. Ed. 2018, 57, 7654.
[6]	Tang, S.-B.; Zhang, X.; Tu, H.-F.; You, S.-L. J. Am. Chem. Soc. 2018, 140, 7737.
[7]	(a) Meng, C.-Y.; Liang, X.; Wei, K.; Yang, Y.-R. Org. Lett. 2019, 21, 840.
	(b) Zhang, T.-Y.; Deng, Y.; Wei, K.; Yang, Y.-R. Org. Lett. 2021, 23, 1086.
[8]	(a) Newton, C. G.; Wang, S.-G.; Oliveira, C. C.; Cramer, N. Chem. Rev. 2017, 117, 8908.
	(b) Chen, Z.; Rong, M.-Y.; Nie, J.; Zhu, X.-F.; Shi, B.-F.; Ma, J.-A. Chem. Soc. Rev. 2019, 48, 4921.
	(c) Gandeepan, P.; Müller, T.; Zell, D.; Cera, G.; Warratz, S.; Ackermann, L. Chem. Rev. 2018, 119, 2192.
	(d) Liu, C.-X.; Yin, S.-Y.; Zhao, F.; Yang, H.; Feng, Z.; Gu, Q.; You, S.-L. Chem. Rev. 2023, 123, 10079.
	(e) Rej, S.; Ano, Y.; Chatani, N. Chem. Rev. 2020, 120, 1788.
	(f) Chu, J. C.; Rovis, T. Angew. Chem. Int. Ed. 2018, 57, 62.
	(g) Wang, R.; Luan, Y.; Ye, M. Chin. J. Chem. 2019, 37, 720.
[9]	(a) Castellino, N. J.; Montgomery, A. P.; Danon, J. J.; Kassiou, M. Chem. Rev. 2023, 123, 8127.
	(b) Burman, J. S.; Blakey, S. B. Angew. Chem. Int. Ed. 2017, 56, 13666.
	(c) Knecht, T.; Mondal, S.; Ye, J.-H.; Das, M.; Glorius, F. Angew. Chem. Int. Ed. 2019, 58, 7117.
	(d) Sihag, P.; Jeganmohan, M. Chem. Commun. 2021, 57, 6428.
	(e) Lei, H.; Rovis, T. J. Am. Chem. Soc. 2019, 141, 2268.
	(f) Guillemard, L.; Kaplaneris, N.; Ackermann, L.; Johansson, M. J. Nat. Rev. Chem. 2021, 5, 522.
	(g) Lerchen, A.; Knecht, T.; Koy, M.; Ernst, J. B.; Bergander, K.; Daniliuc, C. G.; Glorius, F. Angew. Chem. Int. Ed. 2018, 57, 15248.
	(h) Fernandes, R. A.; Nallasivam, J. L. Org. Biomol. Chem. 2019, 17, 8647.
	(i) Manoharan, R.; Jeganmohan, M. Eur. J. Org. Chem. 2020, 7304.
	(j) Jana, R.; Begam, H. M.; Dinda, E. Chem. Commun. 2021, 57, 10842.
[10]	Sihag, P.; Chakraborty, T.; Jeganmohan, M. Org. Lett. 2023, 25, 1257.
[11]	Ye, B.; Cramer, N. J. Am. Chem. Soc. 2013, 135, 636.
[12]	Baik, M. H.; Blakey, S. B. J. Am. Chem. Soc. 2020, 142, 5842.
[13]	Farr, C. M. B.; Kazerouni, A. M.; Park, B.; Poff, C. D.; Won, J.; Sharp, K. R.; Baik, M. H.; Blakey, S. B. J. Am. Chem. Soc. 2020, 142, 13996.

Entry	Rh	Solvent	AgSbF₆ (equiv.)	Yield/%	ee/%	B/L
1	Rh-1	TFE	0.1	42	56	1.5∶1
2	Rh-2	TFE	0.1	25	15	1.1∶1
3	Rh-3	TFE	0.1	20	35	1.3∶1
4	Rh-4	TFE	0.1	35	49	2.4∶1
5	Rh-5	TFE	0.1	32	51	2.1∶1
6	Rh-1	HFIP	0.1	43	40	2.8∶1
7	Rh-1	DCE	0.1	48	37	2.2∶1
8	Rh-1	MeOH	0.1	48	54	1.2∶1
9	Rh-1	TFE	—	NR	—	—
10	Rh-1	TFE	1.0	60	70	3.2∶1
11	Rh-1	TFE	2.0	71	87	3.3∶1
12	Rh-1	TFE	2.5	68	87	3.2∶1

Entry	Rh	Solvent	AgSbF₆ (equiv.)	Yield/%	ee/%	B/L
1	Rh-1	TFE	0.1	42	56	1.5∶1
2	Rh-2	TFE	0.1	25	15	1.1∶1
3	Rh-3	TFE	0.1	20	35	1.3∶1
4	Rh-4	TFE	0.1	35	49	2.4∶1
5	Rh-5	TFE	0.1	32	51	2.1∶1
6	Rh-1	HFIP	0.1	43	40	2.8∶1
7	Rh-1	DCE	0.1	48	37	2.2∶1
8	Rh-1	MeOH	0.1	48	54	1.2∶1
9	Rh-1	TFE	—	NR	—	—
10	Rh-1	TFE	1.0	60	70	3.2∶1
11	Rh-1	TFE	2.0	71	87	3.3∶1
12	Rh-1	TFE	2.5	68	87	3.2∶1

[1]	Xueying Yang, Yuanshuang Xu, Xinying Zhang, Xuesen Fan. Synthesis of C2-Spiroindolines Based on the Cascade Reaction of 2-Aryl-3H-indoles with Cyclopropanols [J]. Chinese Journal of Organic Chemistry, 2025, 45(2): 694-706.
[2]	Junfeng Yang, Yanqiu Zhao, Lei Shi. Electron Donor-Acceptor (EDA) Complex-Driven Activation of N-α C—H Bonds [J]. Chinese Journal of Organic Chemistry, 2025, 45(2): 559-573.
[3]	Manman Wang, Wenhui Xi, Hao Wu, Dachang Bai. Recent Advances in Transition-Metal Catalyzed C—H Bond Activation for the Synthesis of C(sp³)-Fluoroalkyl Compounds [J]. Chinese Journal of Organic Chemistry, 2025, 45(2): 516-530.
[4]	Chaowei Zhang, Bingbin Xu, Wenlong Liu, Jing Zhao, Weiliang Duan. Palladium-Catalyzed Asymmetric C—H Activation for the Synthesis of Planar Chiral Ferrocene Sulfonamides [J]. Chinese Journal of Organic Chemistry, 2025, 45(2): 707-716.
[5]	Fan Yang, Xiaomeng Fan, Xuejing Yao, Ruijie Mi, Songjie Yu, Xingwei Li, Jian Xiao. Rhodium(III)-Catalyzed Annulative Coupling between Sulfoxonium Ylides and Diazo Compounds [J]. Chinese Journal of Organic Chemistry, 2025, 45(1): 331-342.
[6]	Jia-Xi Jiang, Quan-Zhong Liu. Non-Metallic Carbene Pathway Transformations of Vinyl Diazo Compounds [J]. Chinese Journal of Organic Chemistry, 2024, 44(9): 2640-2657.
[7]	Guotao Lin, Jian Xu, Qiuling Song. Recent Advances in the Synthesis of P-Stereogenic Compounds via Desymmetrization Strategy [J]. Chinese Journal of Organic Chemistry, 2024, 44(12): 3621-3638.
[8]	Youlong Du, Qian Wang, Haibo Mei, Romana Pajkert, Gerd-Volker Röschenthaler, Jianlin Han. Recent Advances on the Synthesis and Application of α,α-Difluoro-β-aminophosphonates [J]. Chinese Journal of Organic Chemistry, 2024, 44(12): 3686-3701.
[9]	Yuying Liu, Zhanwei Fu, Chao Yang, Mupeng Luo, Shurong Ban, Shouguo Wang. Rh(III)-Catalyzed Aminoalkylation of Alkenes with Diazo Compounds toward Functionalized Isoindolinones [J]. Chinese Journal of Organic Chemistry, 2024, 44(11): 3505-3517.
[10]	Xiaoyang Gao, Ruirui Zhai, Xun Chen, Shuojin Wang. Recent Progress in C—H Bond Activation Reaction with Vinylene Carbonate [J]. Chinese Journal of Organic Chemistry, 2023, 43(9): 3119-3134.
[11]	Xiaoping Xu, Yifei Zhang, Xiaoyu Mo, Jun Jiang. Rh-Catalyzed C—H Functionalization Reaction between 3-Diazoindolin-2-imines and Pyrazolones for the Construction of 3-Pyrazolyl Indoles [J]. Chinese Journal of Organic Chemistry, 2023, 43(7): 2519-2527.
[12]	Zhicheng Bao, Muyao Li, Jianbo Wang. Copper-Catalyzed Cross-Coupling of Aryldiazoacetates with Bis[(pinacolato)boryl]methane [J]. Chinese Journal of Organic Chemistry, 2023, 43(5): 1808-1814.
[13]	Kongchuan Wu, Kaihong Lu, Jianbin Lin, Huijun Zhang. Research Progress in Ortho-C—H Bond Functionalization of Rylene Diimides [J]. Chinese Journal of Organic Chemistry, 2023, 43(3): 1000-1011.
[14]	Fang Wang, Lei Wang. Recent Advances in Functionalization of Aromatic C(sp²)—H Bonds Based on N-Nitroso Direction [J]. Chinese Journal of Organic Chemistry, 2023, 43(12): 4157-4167.
[15]	Meijiao Sun, Jing Tan, Yu Tan, Jinsong Peng, Chunxia Chen. Pd-Catalyzed C(2)—H Arylation of 3-(2-Aminopyrimidin-4-yl)indoles [J]. Chinese Journal of Organic Chemistry, 2023, 43(11): 3945-3959.

铑(III)催化的非活化烯烃与α-重氮羰基化合物的对映选择性烯丙位C—H键烷基化反应

Rhodium(III)-Catalyzed Enantioselective Allylic C—H Alkylation of Unactivated Alkenes with α‑Diazocarbonyl Compounds

RichHTML

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 7

References 13

Related Articles 15

Recommended Articles

Metrics

Comments