Cu/Chiral Phosphoric Acid-Catalyzed Asymmetric Radical-Initiated Aminoarylation of Alkenes

doi:10.6023/A18100413

Acta Chimica Sinica ›› 2018, Vol. 76 ›› Issue (11): 878-882.DOI: 10.6023/A18100413 Previous Articles Next Articles

Special Issue: 有机小分子-金属协同催化

Communication

铜/手性磷酸催化烯烃不对称自由基胺芳基化

李雪飞^a, 林进顺^a, 王建^a, 李忠良^b, 顾强帅^b, 刘心元^a

a. 南方科技大学化学系深圳市格拉布斯研究所深圳 518055;
b. 南方科技大学前沿与交叉科学研究院深圳 518055

投稿日期:2018-10-07 发布日期:2018-10-15
通讯作者: 顾强帅, 刘心元 E-mail:guqs@sustc.edu.cn;liuxy3@sustc.edu.cn
基金资助:
项目受国家自然科学基金（Nos.21722203，21572096）、深圳市科技研发资金（Nos.JCYJ20170412152435366，JCYJ20170307105638498）和深圳市诺贝尔奖科学家实验室（No.C17213101）资助.

Cu/Chiral Phosphoric Acid-Catalyzed Asymmetric Radical-Initiated Aminoarylation of Alkenes

Li Xue-Fei^a, Lin Jin-Shun^a, Wang Jian^a, Li Zhong-Liang^b, Gu Qiang-Shuai^b, Liu Xin-Yuan^a

a. Department of Chemistry and Shenzhen Grubbs Institute, Southern University of Science and Technology, Shenzhen 518055;
b. SUSTech Academy for Advanced Interdisciplinary Studies, Southern University of Science and Technology, Shenzhen 518055

Received:2018-10-07 Published:2018-10-15
Contact: 10.6023/A18100413 E-mail:guqs@sustc.edu.cn;liuxy3@sustc.edu.cn
Supported by:
Project supported by the National Natural Science Foundation of China (Nos. 21722203, 21572096), the Shenzhen Special Funds (Nos. JCYJ20170412152435366, JCYJ20170307105638498) and the Shenzhen Nobel Prize Scientists Laboratory Project (No. C17213101).

1. Cu/Chiral Phosphoric Acid-Catalyzed Asymmetric Radical-Initiated Aminoarylation of Alkenes.PDF(8982KB)

Abstract

Enantioenriched pyrrolidines bearing a β-aryl group and an α-quaternary carbon stereocenter are important structural motifs in many natural products and pharmaceuticals, and their enantioselective synthesis has thus received extensive attention over the last several decades. Nonetheless, so far as we know, asymmetric aminoarylation of alkenes to access such targets has only been independently reported by Wolfe and Liu using palladium catalysis involving a key aminopalladation step, and thus, general and practical methodologies towards a variety of chiral pyrrolidines are still in demand and highly desirable. As part of our ongoing interest in radical-initiated difunctionalization reactions of alkenes based on Cu(I)/chiral phosphoric acid (CPA) catalysis, we sought to develop a mechanistically distinct and complementary approach for this asymmetric palladium(Ⅱ)-catalyzed aminoarylation of alkenes. Herein we describe our efforts toward the development of the efficient asymmetric radical-initiated aminoarylation of alkenes with aryldiazonium salts enabled by Cu(I)/CPA catalysis. A general procedure for the aminoarylation of alkenes with aryldiazonium salts is as follows:under argon, an oven-dried resealable Schlenk tube equipped with a magnetic stir bar was charged with urea substrate 1 (0.1 mmol, 1.0 equiv.), CuI (1.9 mg, 0.01 mmol, 10 mol%), CPA[(S)-A1 (9.3 mg, 0.015 mmol, 15 mol%], aryldiazonium salts 2 (0.12 mmol, 1.2 equiv.), Na₃PO₄ (19.7 mg, 0.12 mmol, 1.2 equiv.) and isopropyl acetate(1.0 mL) at 32℃ and the sealed tube was then stirred under the same conditions. Upon completion (monitored by thin-layer chromatography), the reaction mixture was directly purified by silica gel chromatography[eluent:V(petroleum ether):V(EtOAc)=100:0 to 3:1] to afford the desired product 3. The enantiometric excess of product was determined by chiral high-performance liquid chromatography (HPLC) analysis. A broad scope of substrates worked well under this standard conditions to afford enantioenriched pyrrolidines in good yield with good to excellent enantioselectivity. A series of control experiments were conducted to determine the reaction mechanism as a radical process and a possible mechanism was proposed.

Key words: copper catalysis, chiral phosphoric acid, radical, aryldiazonium salts, asymmetric aminoarylation

Cite this article

Li Xue-Fei, Lin Jin-Shun, Wang Jian, Li Zhong-Liang, Gu Qiang-Shuai, Liu Xin-Yuan. Cu/Chiral Phosphoric Acid-Catalyzed Asymmetric Radical-Initiated Aminoarylation of Alkenes[J]. Acta Chimica Sinica, 2018, 76(11): 878-882.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

References

[1] (a) Royles, B. J. L. Chem. Rev. 1995, 95, 1981;
(b) O'Hagan, D. Nat. Prod. Rep. 2000, 17, 435.
(c) Lewis, J. R. Nat. Prod. Rep. 2001, 18, 95.
(d) Fish, P. V.; Andrews, M. D.; Jonathan Fray, M.; Stobie, A.; Wakenhut, F.; Whitlock, G. A. Bioorg. Med. Chem. Lett. 2009, 19, 2829.
[2] (a) Fache, F.; Schulz, E.; Tommasino, M. L.; Lemaire, M. Chem. Rev. 2000, 100, 2159.
(b) Notz, W.; Tanaka, F.; Barbas, C. F. Acc. Chem. Res. 2004, 37, 580.
(c) Erkkila, A.; Majander, I.; Pihko, P. M. Chem. Rev. 2007, 107, 5416.
(d) Caputo, C. A.; Jones, N. D. Dalton Trans. 2007, 4627.
[3] (a) Pettit, G. R.; Goswami, A.; Cragg, G. M.; Schmidt, J. M.; Zou, J. C. J. Nat. Prod. 1984, 47, 913.
(b) Su, B.; Cai, C.; Deng, M.; Wang, Q. J. Agric. Food. Chem. 2016, 64, 2039.
[4] Oloff, S.; Mailman, R. B.; Tropsha, A. J. Med. Chem. 2005, 48, 7322.
[5] Burnett, D. A.; Hart, D. J. J. Org. Chem. 1987, 52, 5662.
[6] Lebon, F.; Pegurier, C.; Ledecq, M.; Mathieu, B.; Bosman, N.; Frycia, A.; Lengele, S.; Dhurke, K.; Kanduluru, A. K.; Meunier, S.; Wagner, A.; Wolff, C.; Provins, L. Bioorg. Med. Chem. Lett. 2012, 22, 3978.
[7] For selected reviews, see:(a) Coldham, I.; Hufton, R. Chem. Rev. 2005, 105, 2765.
(b) Pandey, G.; Banerjee, P.; Gadre, S. R. Chem. Rev. 2006, 106, 4484.
(c) Pellissier, H. Tetrahedron 2007, 63, 3235.
(d) Nicolle, S. M.; Lewis, W.; Hayes, C. J.; Moody, C. J. Angew. Chem., Int. Ed. 2016, 55, 3749.
[8] For selected racemic examples, see:(a) Ney, J. E.; Wolfe, J. P. Angew. Chem., Int. Ed. 2004, 43, 3605.
(b) Ney, J. E.; Hay, M. B.; Yang, Q.; Wolfe, J. P. Adv. Synth. Catal. 2005, 347, 1614.
(c) Bertrand, M. B.; Leathen, M. L.; Wolfe, J. P. Org. Lett. 2007, 9, 457.
(d) Bertrand, M. B.; Neukom, J. D.; Wolfe, J. P. J. Org. Chem. 2008, 73, 8851.
(e) Brenzovich, W. E., Jr.; Benitez, D.; Lackner, A. D.; Shunatona, H. P.; Tkatchouk, E.; Goddard, W. A., 3rd; Toste, F. D. Angew. Chem., Int. Ed. 2010, 49, 5519.
(f) Tkatchouk, E.; Mankad, N. P.; Benitez, D.; Goddard, W. A., 3rd; Toste, F. D. J. Am. Chem. Soc. 2011, 133, 14293.
(g) Fumagalli, G.; Boyd, S.; Greaney, M. F. Org. Lett. 2013, 15, 4398.
(h) Sahoo, B.; Hopkinson, M. N.; Glorius, F. J. Am. Chem. Soc. 2013, 135, 5505.
(i) Fornwald, R. M.; Fritz, J. A.; Wolfe, J. P. Chem.-Eur. J. 2014, 20, 8782.
(j) Alicea, J.; Wolfe, J. P. J. Org. Chem. 2014, 79, 4212.
(k) Faulkner, A.; Scott, J. S.; Bower,
J. F. J. Am. Chem. Soc. 2015, 137, 7224.
(l) Peterson, L. J.; Wolfe, J. P. Adv. Synth. Catal. 2015, 357, 2339.
(m) Garad, D. N.; Mhaske, S. B. Org. Lett. 2016, 18, 3862.
(n) Yang, H.-B.; Pathipati, S. R.; Selander, N. ACS Catal. 2017, 7, 8441.
(o) Yang, M.-N.; Yan, D.-M.; Zhao, Q.-Q.; Chen, J.-R.; Xiao, W.-J. Org. Lett. 2017, 19, 5208.
(p) Zhang, R.; Xu, Q.; Shi, M. Acta Chim. Sinica 2012, 70, 1593. (张睿, 徐琴, 施敏, 化学学报, 2012, 70, 1593.)
(q) Zhang, J.; Wu, Z.; Xie, F.; Zhang, W. Chin. J. Org. Chem. 2018, 38, 1319. (张金刚, 吴正兴, 谢芳, 张万斌, 有机化学, 2018, 38, 1319.)
[9] For selected reviews, see:(a) Heinrich, M. R. Chem. Eur. J. 2009, 15, 820.
(b) Hari, D. P.; Koenig, B. Angew. Chem., Int. Ed. 2013, 52, 4734.
(c) Kindt, S.; Heinrich, M. R. Synthesis 2016, 48, 1597.
[10] For selected examples, see:(a) Sahoo, B.; Hopkinson, M. N.; Glorius, F. J. Am. Chem. Soc. 2013, 135, 5505.
(b) Hari, D. P.; Hering, T.; Koenig, B. Angew. Chem., Int. Ed. 2014, 53, 725.
(c) Kindt, S.; Wicht, K.; Heinrich, M. R. Org. Lett. 2015, 17, 6122.
[11] (a) Mai, D. N.; Wolfe, J. P. J. Am. Chem. Soc. 2010, 132, 12157.
(b) Babij, N. R.; Wolfe, J. P. Angew. Chem., Int. Ed. 2013, 52, 9247.
(c) Hopkins, B. A.; Wolfe, J. P. Chem. Sci. 2014, 5, 4840.
(d) White, D. R.; Hutt, J. T.; Wolfe, J. P. J. Am. Chem. Soc. 2015, 137, 11246.
(e) Garlets, Z. J.; Parenti, K. R.; Wolfe, J. P. Chem.-Eur. J. 2016, 22, 5919.
[12] Zhang, W.; Chen, P.; Liu, G. Angew. Chem., Int. Ed. 2017, 56, 5336.
[13] (a) Neukom, J. D.; Perch, N. S.; Wolfe, J. P. J. Am. Chem. Soc. 2010, 132, 6276.
(b) Neukom, J. D.; Perch, N. S.; Wolfe, J. P. Organometallics 2011, 30, 1269.
[14] Zhu, R.; Buchwald, S. L. J. Am. Chem. Soc. 2015, 137, 8069.
[15] Lin, J.-S.; Dong, X.-Y.; Li, T.-T.; Jiang, N.-C.; Tan, B.; Liu, X.-Y. J. Am. Chem. Soc. 2016, 138, 9357.
[16] Lin, J.-S.; Wang, F.-L.; Dong, X.-Y.; He, W.-W.; Yuan, Y.; Chen, S.; Liu, X.-Y. Nat. Commun. 2017, 8, 14841.
[17] Wang, F.-L.; Dong, X.-Y.; Lin, J.-S.; Zeng, Y.; Jiao, G.-Y.; Gu, Q.-S.; Guo, X.-Q.; Ma, C.-L.; Liu, X.-Y. Chem 2017, 3, 979.
[18] (a) Wang, F.; Wang, D.; Wan, X.; Wu, L.; Chen, P.; Liu, G. J. Am. Chem. Soc. 2016, 138, 15547.
(b) Wang, D.; Wang, F.; Chen, P.; Lin, Z.; Liu, G. Angew. Chem., Int. Ed. 2017, 56, 2054.
(c) Wu, L.; Wang, F.; Wan, X.; Wang, D.; Chen, P.; Liu, G. J. Am. Chem. Soc. 2017, 139, 2904.
[19] Cheng, Y.-F.; Dong, X.-Y.; Gu, Q.-S.; Yu, Z.-L.; Liu, X.-Y. Angew. Chem., Int. Ed. 2017, 56, 8883.

铜/手性磷酸催化烯烃不对称自由基胺芳基化

Cu/Chiral Phosphoric Acid-Catalyzed Asymmetric Radical-Initiated Aminoarylation of Alkenes

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Shan Li, Junxin Lu, Jie Liu, Lvqi Jiang, Wenbin Yi. Electrochemical Synthesis of α-Fluoroalkylated Ketones using Sodium Fluoroalkylsulfinate [J]. Acta Chimica Sinica, 2024, 82(2): 110-114.
[2]	Yaning Li, Xiaoyan Wang, Yong Tang. The Regulation of Stereoselectivity in Radical Polymerization^★ [J]. Acta Chimica Sinica, 2024, 82(2): 213-225.
[3]	Jinglin Yi, Mao Chen. Photo-Induced Copolymerization of Chlorotrifluoroethylene and Methyl Isopropenyl Ether^★ [J]. Acta Chimica Sinica, 2024, 82(2): 126-131.
[4]	Shenna Deng, Changchun Peng, Yunhong Niu, Yun Xu, Yunxiao Zhang, Xiang Chen, Hongmin Wang, Shanshan Liu, Xiao Shen. Radical Brook Rearrangement Mediated Olefin Difunctionalization Involving α-Fluoroalkyl-α-silyl Methanols [J]. Acta Chimica Sinica, 2024, 82(2): 119-125.
[5]	Jianqiang Chen, Gangguo Zhu, Jie Wu. Recent Advances in Nickel-Catalyzed Ring Opening Cross-Coupling of Aziridines [J]. Acta Chimica Sinica, 2024, 82(2): 190-212.
[6]	Zhanglong Yu, Zhongliang Li, Changjiang Yang, Qiangshuai Gu, Xinyuan Liu. Research Progress on Copper-Catalyzed Enantioselective Desymmetrization of Diols^★ [J]. Acta Chimica Sinica, 2023, 81(8): 955-966.
[7]	Yanyan Ren, Xin Li, Yingfeng Han. Synthesis and Optical Property Studies of Blue-Light Organic Radicals Based on N-Heterocyclic Carbenes^★ [J]. Acta Chimica Sinica, 2023, 81(7): 735-740.
[8]	Li Liu, Gang Zheng, Guoqiang Fan, Hongguang Du, Jiajing Tan. Research Progress in Organic Reactions Involving 4-Acyl/Carbamoyl/Alkoxycarbonyl Substituted Hantzsch Esters [J]. Acta Chimica Sinica, 2023, 81(6): 657-668.
[9]	Jie Yang, Lin Ling, Yuxue Li, Long Lu. Density Functional Theory Study on Thermal Decomposition Mechanisms of Ammonium Perchlorate [J]. Acta Chimica Sinica, 2023, 81(4): 328-337.
[10]	Yating Zhao, Fan Liu, Qiuan Wang, Wujiong Xia. Visible-Light-Promoted N-Alkylation Reactions of (aza)Aromatic Amines with Ethyl Diazoacetate [J]. Acta Chimica Sinica, 2023, 81(2): 111-115.
[11]	Jianqiang Chen, Gangguo Zhu, Jie Wu. Recent Advances in Radical-Based Dehydroxylation of Hydroxyl Groups via Oxalates [J]. Acta Chimica Sinica, 2023, 81(11): 1609-1623.
[12]	Kongxi Qiu, Jie Li, Haowen Ma, Wei Zhou, Qian Cai. Recent Advances in the Construction of Nitrogen-Containing Heterocycles via Trapping Organocopper(I) Intermediates [J]. Acta Chimica Sinica, 2023, 81(1): 42-63.
[13]	Hongdan Zhang, Xinyu Lan, Peng Cheng. Advances in Hydroxyl Free Radical Assisted Synthesis of Zeolite [J]. Acta Chimica Sinica, 2023, 81(1): 100-110.
[14]	Xiaojuan Li, Ziyu Ye, Shuhan Xie, Yongjing Wang, Yonghao Wang, Yuancai Lv, Chunxiang Lin. Study on Performance and Mechanism of Phenol Degradation through Peroxymonosulfate Activation by Nitrogen/Chlorine Co-doped Porous Carbon Materials [J]. Acta Chimica Sinica, 2022, 80(9): 1238-1249.
[15]	Guanglu Yue, Jingyao Wei, Di Qiu, Fanyang Mo. Recent Advances in the Synthesis of Arylstannanes [J]. Acta Chimica Sinica, 2022, 80(7): 956-969.