Palladium-Catalyzed Oxidative Aminofluorination of Styrenes

doi:10.6023/A12100835

Acta Chimica Sinica ›› 2012, Vol. 70 ›› Issue (23): 2404-2407.DOI: 10.6023/A12100835 Previous Articles Next Articles

Communications

钯催化苯乙烯类分子胺氟化反应研究

朱海涛, 刘国生

金属有机化学国家重点实验室中国科学院上海有机化学研究所上海 200032

投稿日期:2012-10-29 发布日期:2012-11-12
通讯作者: 刘国生 E-mail:gliu@mail.sioc.ac.cn
基金资助:
项目受科技部973 (No. 2009CB825300);国家自然科学基金(Nos. 0972175, 20923005)和上海市科委(No. 11JC1415000)资助.

Palladium-Catalyzed Oxidative Aminofluorination of Styrenes

Zhu Haitao, Liu Guosheng

State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032

Received:2012-10-29 Published:2012-11-12
Supported by:
Project supported by the 973 Program of China (No. 2009CB825300), the National Natural Science Foundation of China (Nos. 20972175, 20923005), and the Science and Technology Commission of the Shanghai Municipality (No. 11JC1415000).

1. Palladium-Catalyzed Oxidative Aminofluorination of Styrenes.PDF(493KB)

Abstract

A novel palladium-catalyzed intermolecular aminofluorination of styrenes has been developed, using silver fluoride as the fluorine source, palladium diacetate as metal catalyst, and acetonitrile as solvent at room temperature. As regard to the mechanism, we proposed that the anti-Markovnikov aminopalladation was involved in the construction of C—N bond. This selectivity of nucleophilic palladation of styrenes is different from that reported before. In order to verify our proposed mechanism, we conducted the competition experiments using styrenes containing different functional groups. The results are consistent with our analysis. We belive that the C—F bond is formed after the Pd(II)-C is oxidized to Pd(IV)-C. Namely, the high oxidative state palladium is involved in catalytic cycle. In all, this transformation represents a novel strategy to synthesize a variety of vicinal fluoroamine derivatives.

Key words: palladium, aminofluorination, anti-Markovnikov, styrene

Cite this article

Zhu Haitao, Liu Guosheng. Palladium-Catalyzed Oxidative Aminofluorination of Styrenes[J]. Acta Chimica Sinica, 2012, 70(23): 2404-2407.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

References

[1] (a) Welch, J. T.; Eswarakrishman, S. Fluorine in Bioorganic Chemistry, Wiley, New York, 1991;
(b) Banks, R. E.; Smart, B. E.; Tatlow, J. C. Organofluorine Chemistry, Principles and Commercial Application, Plenum Press, New York, 1994.
[2] For reviews on fluorination of organic compounds, see (a) Nyffeler, P. T.; Duron, S. G.; Burkart, M. D.; Vincent, S. P.; Wong, C. H. Angew. Chem. Int. Ed. 2005, 44, 192;
(b) Shimizu, M.; Hiyama, T. Angew. Chem. Int. Ed. 2005, 44, 214;
(c) Pihko, P. M. Angew. Chem. Int. Ed. 2006, 45, 544;
(d) Appayee, C.; Brenner-Moyer, S. E. Org. Lett. 2010, 12, 3357.
[3] (a) Smoekh, L.; Shanzer, A. J. Am. Chem. Soc. 1982, 104, 5836;
(b) Philips, A. J.; Uto, Y.; Wipf, P.; Reno, M. J.; Williams, D. R. Org. Lett. 2000, 2, 1165;
(c) Li, Y.; Ni, C.; Liu, J.; Zhang, L.; Zheng, J.; Zhu, L.; Hu, J. Org. Lett. 2006, 8, 1693;
(d) Anbarasan, P.; Neumann, H.; Beller, M. Angew. Chem. Int. Ed. 2010, 49, 2219;
(e) Wilson, D. A. US 4339070, 1983 [Chem. Abstr. 1983, 99, 138839].
[4] For some reviews, see: (a) Müller, T. E.; Beller, M. Chem. Rev. 1998, 98, 675;
(b) Brunet, J. J.; Togni, A.; Grützmacher, D. H. Catalytic Heterofunctionalization, Wiley-VCH, New York, 2001, pp. 91～141;
(c) Eds.: Hong, S.; Marks, T. J. Acc. Chem. Res. 2004, 37, 673;
(d) Hartwig, J. F. Pure Appl. Chem. 2004, 76, 507.
[5] For reviews that describe oxidative amination reaction, see: (a) Beccalli, E. M.; Broggini, G.; Marttinelli, M.; Sottocornola, S. Chem. Rev. 2007, 107, 5318;
(b) Stahl, S. S. Angew. Chem. Int. Ed. 2004, 43, 3400;
(c) Kotov, V.; Scarborough, C. C.; Stahl, S. S. Inorg. Chem. 2007, 46, 1910;
(d) McDonald, R. I.; Liu, G. S.; Stahl, S. S. Chem. Rev. 2011, 111, 2981.
[6] For some examples of intermolecular oxidative amination of alkenes, see: (a) Timokhin, V. I.; Anastasi, N. R.; Stahl, S. S. J. Am. Chem. Soc. 2003, 125, 12996;
(b) Brice, J. L.; Harang, J. E.; Timokhin, V. I.; Anastasi, N. R.; Stahl, S. S. J. Am. Chem. Soc. 2005, 127, 2868;
(c) Timokhin, V. I.; Stahl, S. S. J. Am. Chem. Soc. 2005, 127, 17888.
[7] For recent reviews on transition metal-catalyzed C-F bond formation, see: (a) Brown, J. M.; Gouvernuer, V. Angew. Chem. Int. Ed. 2009, 48, 8610;
(b) Grushin, V. V. Acc. Chem. Res. 2010, 43, 160;
(c) Furuya, T.; Klein, J. E. M. N.; Ritter, T. Synthesis 2010, 1804. For recent examples see:
(d) Hull, K. L.; Anani, W. Q.; Sanford, M. S. J. Am. Chem. Soc. 2006, 128, 7134;
(e) Wang, X.; Mei, T. S.; Yu, J. Q. J. Am. Chem. Soc. 2009, 131, 7520;
(f) Furuya, T.; Kaiser, H. M.; Ritter, T. Angew. Chem., Int. Ed. 2008, 47, 5993;
(g) Watson, D. A.; Su, M.; Teverovskiy, G.; Zhang, Y.; García-Fortanet, J.; Kinzel, T.; Bulchwald, S. L. Science 2009, 325, 1661;
(h) Tang, P.; Furuya, T.; Ritter, T. J. Am. Chem. Soc. 2010, 132, 12150.
[8] Qiu, S.; Xu, T.; Zhou, J.; Guo, Y.; Liu, G. J. Am. Chem. Soc. 2010, 132, 2856.
[9] Wu, T.; Yin, G.; Liu, G. J. Am. Chem. Soc. 2009, 131, 16354.
[10] The effect of silver is unclear at this moment. It is possible that AgF is effective for the generation of C-PdF complex via the interaction of Ag and Pd. For details, see: (a) Heckenroth, M.; Neels, A.; Garnier, M. G.; Aebi, P.; Ehlers, A. W.; Albrecht, M. Chem. Eur. J. 2009, 15, 9375;
(b) Heckenroth, M.; Kluser, E.; Neels, A.; Albrecht, M. Angew. Chem., Int. Ed. 2007, 46, 6293.
[11] (a) Gatti, G.; López, J. A.; Mealli, C.; Musco, A. J. Organomet. Chem. 1994, 483, 77;
(b) Rix, F. C.; Brookhart, M.; White, P. S. J. Am. Chem. Soc. 1996, 118, 2436;
(c) LaPoite, A. M.; Rix, F. C.; Brookhart, M. J. Am. Chem. Soc. 1997, 119, 906;
(d) Lin, Y. S.; Yamamoto, A. Organometallics 1998, 17, 3466;
(e) Nozaki, K.; Komaki, H.; Kawashima, Y.; Hiyama, T.; Matsubara, T. J. Am. Chem. Soc. 2001, 123, 534;
(f) Hii, K. K.; Claridge, T. D. W.; Giernoth, R.; Brown, J. M. Adv. Synth. Catal. 2004, 346, 983.

[1]	Dawei Zhang, Haiyang Zhao, Xiaotian Feng, Yucheng Gu, Xingang Zhang. Palladium-Catalyzed Cross-Coupling of Heteroaryl Bromides with gem-Difluoroallylborons [J]. Acta Chimica Sinica, 2024, 82(2): 105-109.
[2]	Yeqiang Han, Bingfeng Shi. Palladium(II)-Catalyzed Enantioselective Functionalization of C(sp³)—H Bonds^★ [J]. Acta Chimica Sinica, 2023, 81(11): 1522-1540.
[3]	Chunhui Yang, Jingchao Chen, Xinhan Li, Li Meng, Kaimin Wang, Weiqing Sun, Baomin Fan. Difluoroallylation of Silanes under Photoirradiation [J]. Acta Chimica Sinica, 2023, 81(1): 1-5.
[4]	Yixiu Ge, Zaozao Qiu, Zuowei Xie. Pd-Catalyzed One-Pot Synthesis of Difunctionalized o-Carboranes via Construction of B—C and B—Heteroatom Bonds^※ [J]. Acta Chimica Sinica, 2022, 80(4): 432-437.
[5]	Yunfang Xu, Yang Li, Zitong Fu, Shaoyan Lin, Jie Zhu, Lei Wu. Palladium-catalyzed Stereoselective Synthesis of (Z)-[3]Dendralenes [J]. Acta Chimica Sinica, 2022, 80(10): 1369-1375.
[6]	Bo Zhou, Renxiao Liang, Zhongyan Cao, Pinghai Zhou, Yixia Jia. Palladium-Catalyzed Heck Reaction of Endocyclic Conjugated C=C Bonds of Pyrroles [J]. Acta Chimica Sinica, 2021, 79(2): 176-179.
[7]	Liu Qingqing, Zhang Yihan, Gao Can, Wang Tianyu, Hu Wenping, Dong Huanli. Synthesis and Property Study of Field-effect Emissive Conjugated Polymers Based on Styrene and Benzothiadiazole [J]. Acta Chimica Sinica, 2020, 78(9): 945-953.
[8]	Huang Hao, Lin Huaxin, Wang Min, Liao Jian. Copper-Catalyzed Enantioselective Aminoboration of Styrenes with 1,2-Benzisoxazole as Nitrogen Source [J]. Acta Chimica Sinica, 2020, 78(11): 1229-1234.
[9]	Li Zhong-Yuan, Jing Kun, Li Qi-Li, Wang Guan-Wu. Palladium-Catalyzed Decarboxylative Coupling of Potassium Oxalate Monoester with 2-Aryloxypyridines [J]. Acta Chim. Sinica, 2019, 77(8): 729-734.
[10]	Luo Jianxin, Yan Wenhai, Ma Qing, Zhang Chunyan, Fang Yiquan, Zhang Xucheng, Wang Changchun. Study on High Activity Monodispersed Sulfonated Porous Polystyrene Microspheres for Preparation of Biodiesel [J]. Acta Chimica Sinica, 2019, 77(1): 54-59.
[11]	Liu Qingyun, Zhao Xianghu, Li Jialu, Cao Song. Synthesis of Cyanated Difluorostyrene Derivatives via S_N2' Cyanomethylation of α-(Trifluoromethyl)styrenes with Acetonitrile [J]. Acta Chim. Sinica, 2018, 76(12): 945-950.
[12]	Zhou Xiao-Le, Su Yong-Liang, Wang Pu-Sheng, Gong Liu-Zhu. Asymmetric Allylic C-H Alkylation of 1,4-Dienes with Aldehydes [J]. Acta Chim. Sinica, 2018, 76(11): 857-861.
[13]	Khan Ijaz, Li Hongfang, Wu Xue, Zhang Yong Jian. Asymmetric Decarboxylative Cycloaddition of Vinylethylene Carbonates with Aldehydes by Cooperative Catalysis of Palladium Complex and Chiral Squaramide [J]. Acta Chim. Sinica, 2018, 76(11): 874-877.
[14]	Zhang Yongling, Wang Min, Cao Peng, Liao Jian. Copper-Catalyzed Enantioselective Aminoboration of Styrenes with Chiral Sulfoxide Phosphine Ligand [J]. Acta Chim. Sinica, 2017, 75(8): 794-797.
[15]	Wang Yifan, Fan Yimei, Jian Jun, Pan Yumin, Zhao Liang, Jing Xueping, Zhou Shengjia, Chen Xiaohong, Du Quan, Wang Ling, Wu Xiaoju, Fu Xiangkai. Synthesis of Chiral Salen Mn (III) Complex Immobilized on Phenoxy-modified AlPS-PVPA as Catalysts for Epoxidation of Olefins [J]. Acta Chim. Sinica, 2017, 75(7): 715-722.

钯催化苯乙烯类分子胺氟化反应研究

Palladium-Catalyzed Oxidative Aminofluorination of Styrenes

PDF

Supporting Info.

Knowledge

Cited

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments