Citation: 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 Chimica Sinica, ;2018, 76(11): 857-861. doi: 10.6023/A18060235 shu

Asymmetric Allylic C-H Alkylation of 1, 4-Dienes with Aldehydes

a.
School of Chemistry and Materials Science, University of Science and Technology of China, Hefei 230026
b.
Hefei National Laboratory for Physical Sciences at the Microscale, Hefei 230026

Corresponding author: Wang Pu-Sheng, pusher@ustc.edu.cn Gong Liu-Zhu, gonglz@ustc.edu.cn
Received Date: 15 June 2018
Available Online: 16 November 2018
Fund Project: the National Natural Science Foundation of China 21502183Project supported by the National Natural Science Foundation of China (Nos. 21502183, 21602214)the National Natural Science Foundation of China 21602214

Figures(3)

In the recent decade, the palladium-catalyzed allylic C-H alkylation reaction of simple alkenes has been well-established as an efficient and atom-economical synthetic alternative for the fine chemical synthesis without the requirement of any prefunctionalization, in comparison with the conventional procedures. We recently established a highly enantioselective α-allylation reaction of enolizable aldehydes with terminal alkenes by using a ternary catalyst system, including palladium, amine, and chiral Brønsted acid, wherein the chiral anion controls the enantioselectivity. Although this protocol provides allylic alkylation products with high levels of enantioselectivity of up to 90% ee, the extension of the optimal conditions to a 1, 4-diene led to a very low regioslectivity. In the presence of a palladium complex, an oxidant and a chiral phosphoric acid, the 1, 4-diene could be smoothly oxidized and principally generated two regiomeric π-vinylallyl-palladium phosphate intermediates, either of which led to different products. Therefore, the simultaneous control of regio-and stereoselectivities in the allylic C-H alkylation reaction of aldehydes with 1, 4-dienes would pose additional challenge in comparison with a similar reaction of allylarenes. Herein, we will report an asymmetric α-allylation of enolizable aldehydes with a wide range of 1, 4-dienes enabled by cooperative catalysis of a palladium complex, amine, and a chiral Brønsted acid. The presence of 6 mol% Pd(OAc)₂, 24 mol% P(4-MeOC₆H₄)₃, 6 mol% chiral phosphoric acid (R)-TRIP, 80 mol% cumylamine and 1.50 equivalents of 2, 6-dimethylbenzoquinone enabled (E)-penta-1, 4-dien-1-ylbenzene (1a) to smoothly undergo the asymmetric allylic C-H alkylation reaction with 2-phenylpropanal (2a), giving rise to the desired α-allylated aldehyde 3a in a 77% isolated yield, 11:1 regioselectivity, 20:1 E/Z and 93% ee. Under the optimal conditions, the generality for enolizable aldehydes was investigated and revealed that 2-aryl propinonaldehydes bearing either electron-donating or electron-withdrawing substituent at the para-(3b~3f) or meta-(3g~3i) position of the phenyl moiety were nicely tolerated, giving rise to the desired allylation products in moderate to good yields with excellent regio-, E/Z-and enantioselectivities. Moreover, 2-naphthyl propinonaldehyde was also able to participate in the asymmetric allylic C-H alkylation reaction, providing the allylation product (3j) with 73% yield, 10:1 regioselectivity, 12:1 E/Z and 91% ee. The examination of 1, 4-dienes found that this protocol tolerated a wide scope of aryl and alkyl substituted 1, 4-dienes, which showed broad adaptability for the facile construction of a broad spectrum of chiral α-quaternary carbonyl compounds. In addition to the terminal aryl-substituted 1, 4-dienes (3k~3q), different substitution patterns were allowed to offer excellent enantioselectivities ranging from 92% ee to 95% ee. Interestingly, this protocol was also amenable to a long chain aliphatic substituent. Although a terminal phenyl (3r) group showed detrimental effect on the regio-and E/Z-selectivities, while the ester (3s), chloride (3t), ether (3u) and cyclohexyl (3v) groups were nicely compatible with the protocol, affording the products with satisfactory results in terms of yields, regio-and stereoselectivities.
- asymmetric catalysis,
- palladium catalysis,
- chiral phosphoric acid,
- 1, 4-diene,
- allylic C-H functionalization
1. [1]
  (a) Corey, E. J.; Guzman-Perez, A. Angew. Chem. Int. Ed. 1998, 37, 388. (b) Trost, B. M.; Jiang, C. Synthesis 2006, 369. (c) Das, J. P.; Marek, I. Chem. Commun. 2011, 47, 4593. (d) Quasdorf, K. W.; Overman, L. E. Nature 2014, 516, 181.
2. [2]
3. [3]
  (a) Hayashi, T. J. Organomet. Chem. 1999, 576, 195. (b) Helmchen, G. J. Organomet. Chem. 1999, 576, 203. (c) Trost, B. M. Chem. Pharm. Bull. 2002, 50, 1. (d) Trost, B. M. J. Org. Chem. 2004, 69, 5813. (e) Trost, B. M.; Machacek, M. R.; Aponick, A. Acc. Chem. Res. 2006, 39, 747.
4. [4]
  (a) Trost, B. M.; Xu, J. J. Am. Chem. Soc. 2005, 127, 2846. (b) Trost, B. M.; Xu, J.; Schmidt, T. J. Am. Chem. Soc. 2009, 131, 18343. (c) Hong, A. Y.; Stoltz, B. M. Eur. J. Org. Chem. 2013, 2013, 2745. (d) Reeves, C. M.; Eidamshaus, C.; Kim, J.; Stoltz, B. M. Angew. Chem. Int. Ed. 2013, 52, 6718.
5. [5]
  (a) Mukherjee, S.; List, B. J. Am. Chem. Soc. 2007, 129, 11336. (b) Jiang, G.; List, B. Angew. Chem. Int. Ed. 2011, 50, 9471. (c) Yoshida, M.; Terumine, T.; Masaki, E.; Hara, S. J. Org. Chem. 2013, 78, 10853. (d) Tao, Z. L.; Zhang, W. Q.; Chen, D. F.; Adele, A.; Gong, L. Z. J. Am. Chem. Soc. 2013, 135, 9255. (e) Wang, P. S.; Lin, H. C.; Zhai, Y. J.; Han, Z. Y.; Gong, L. Z. Angew. Chem. Int. Ed. 2014, 53, 12218. (f) Yoshida, M.; Masaki, E.; Terumine, T.; Hara, S. Synthesis 2014, 46, 1367.
6. [6]
7. [7]
8. [8]
  (a) Trost, B. M.; Thaisrivongs, D. A.; Donckele, E. J. Angew. Chem. Int. Ed. 2013, 52, 1523. (b) Trost, B. M.; Donckele, E. J.; Thaisrivongs, D. A.; Osipov, M.; Masters, J. T. J. Am. Chem. Soc. 2015, 137, 2776.
9. [9]
10. [10]
  (a) Wang, P. S.; Liu, P.; Zhai, Y. J.; Lin, H. C.; Han, Z. Y.; Gong, L. Z. J. Am. Chem. Soc. 2015, 137, 12732. (b) Lin, H. C.; Wang, P. S.; Tao, Z. L.; Chen, Y. G.; Han, Z. Y.; Gong, L. Z. J. Am. Chem. Soc. 2016, 138, 14354. (c) Wang, P. S.; Shen, M. L.; Wang, T. C.; Lin, H. C.; Gong, L. Z. Angew. Chem. Int. Ed. 2017, 56, 16032.
11. [11]
  Tang, S.; Wu, X.; Liao, W.; Liu, K.; Liu, C.; Luo, S.; Lei, A. Org. Lett. 2014, 16, 3584.
12. [12]
  (a) Lacour, J.; Moraleda, D. Chem. Commun. 2009, 7073. (b) Mahlau, M.; List, B. Isr. J. Chem. 2012, 52, 630. (c) Phipps, R. J.; Hamilton, G. L.; Toste, F. D. Nature Chem. 2012, 4, 603. (d) Brak, K.; Jacobsen, E. N. Angew. Chem. Int. Ed. 2013, 52, 534. (e) Mahlau, M.; List, B. Angew. Chem. Int. Ed. 2013, 52, 518.
13. [13]
  (a) Oppolzer, W. Angew. Chem. Int. Ed. Engl. 1984, 23, 876. (b) Yasuda, H.; Nakamura, A. Angew. Chem. Int. Ed. Engl. 1987, 26, 723. (c) Armstrong, S. K. J. Chem. Soc., Perkin Trans. 1 1998, 371. (d) Nicolaou, K. C.; Snyder, S. A.; Montagnon, T.; Vassilikogiannakis, G. Angew. Chem. Int. Ed. 2002, 41, 1668. (e) Takao, K.; Munakata, R.; Tadano, K. Chem. Rev. 2005, 105, 4779.
14. [14]
  (a) Trost, B. M.; Hansmann, M. M.; Thaisrivongs, D. A. Angew. Chem. Int. Ed. 2012, 51, 4950. (b) Trost, B. M.; Thaisrivongs, D. A.; Hansmann, M. M. Angew. Chem. Int. Ed. 2012, 51, 11522.
15. [15]
  (a) Akiyama, T.; Itoh, J.; Yokota, K.; Fuchibe, K. Angew. Chem. Int. Ed. 2004, 43, 1566. (b) Uraguchi, D.; Terada, M. J. Am. Chem. Soc. 2004, 126, 5356. (c) Terada, M. Synthesis 2010, 1929. (d) Yu, J.; Shi, F.; Gong, L. Z. Acc. Chem. Res. 2011, 44, 1156. (e) Wu, H.; He, Y.-P.; Shi, F. Synthesis 2015, 47, 1990.
1. [1]
  Ke QIAO , Yanlin LI , Shengli HUANG , Guoyu YANG . Advancements in asymmetric catalysis employing chiral iridium (ruthenium) complexes. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2091-2104. doi: 10.11862/CJIC.20240265
2. [2]
  Hong Lu , Yidie Zhai , Xingxing Cheng , Yujia Gao , Qing Wei , Hao Wei . Advancements and Expansions in the Proline-Catalyzed Asymmetric Aldol Reaction. University Chemistry, 2024, 39(5): 154-162. doi: 10.3866/PKU.DXHX202310074
3. [3]
  Tingyu Zhu , Hui Zhang , Wenwei Zhang . Exploration and Practice of Ideological and Political Education in the Course of Experiments on Chemical Functional Molecules: Synthesis and Catalytic Performance Study of Chiral Mn(III)Cl-Salen Complex. University Chemistry, 2024, 39(4): 75-80. doi: 10.3866/PKU.DXHX202311011
4. [4]
  Renxiao Liang , Zhe Zhong , Zhangling Jin , Lijuan Shi , Yixia Jia . A Palladium/Chiral Phosphoric Acid Relay Catalysis for the One-Pot Three-Step Synthesis of Chiral Tetrahydroquinoline. University Chemistry, 2024, 39(5): 209-217. doi: 10.3866/PKU.DXHX202311024
5. [5]
  Yan Li , Xinze Wang , Xue Yao , Shouyun Yu . 基于激发态手性铜催化的烯烃E→Z异构的动力学拆分——推荐一个本科生综合化学实验. University Chemistry, 2024, 39(5): 1-10. doi: 10.3866/PKU.DXHX202309053
6. [6]
  Weina Wang , Lixia Feng , Fengyi Liu , Wenliang Wang . Computational Chemistry Experiments in Facilitating the Study of Organic Reaction Mechanism: A Case Study of Electrophilic Addition of HCl to Asymmetric Alkenes. University Chemistry, 2025, 40(3): 206-214. doi: 10.12461/PKU.DXHX202407022
7. [7]
  Qianwen Han , Tenglong Zhu , Qiuqiu Lü , Mahong Yu , Qin Zhong . 氢电极支撑可逆固体氧化物电池性能及电化学不对称性优化. Acta Physico-Chimica Sinica, 2025, 41(1): 2309037-. doi: 10.3866/PKU.WHXB202309037
8. [8]
  Jingzhao Cheng , Shiyu Gao , Bei Cheng , Kai Yang , Wang Wang , Shaowen Cao . 4-氨基-1H-咪唑-5-甲腈修饰供体-受体型氮化碳光催化剂的构建及其高效光催化产氢研究. Acta Physico-Chimica Sinica, 2024, 40(11): 2406026-. doi: 10.3866/PKU.WHXB202406026
9. [9]
  Dongheng WANG , Si LI , Shuangquan ZANG . Construction of chiral alkynyl silver chains and modulation of chiral optical properties. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 131-140. doi: 10.11862/CJIC.20240379
10. [10]
  Jin Tong , Shuyan Yu . Crystal Engineering for Supramolecular Chirality. University Chemistry, 2024, 39(3): 86-93. doi: 10.3866/PKU.DXHX202308113
11. [11]
  Danqing Wu , Jiajun Liu , Tianyu Li , Dazhen Xu , Zhiwei Miao . Research Progress on the Simultaneous Construction of C—O and C—X Bonds via 1,2-Difunctionalization of Olefins through Radical Pathways. University Chemistry, 2024, 39(11): 146-157. doi: 10.12461/PKU.DXHX202403087
12. [12]
  Haiying Wang , Andrew C.-H. Sue . How to Visually Identify Homochiral Crystals. University Chemistry, 2024, 39(3): 78-85. doi: 10.3866/PKU.DXHX202309004
13. [13]
  Keying Qu , Jie Li , Ziqiu Lai , Kai Chen . Unveiling the Mystery of Chirality from Tartaric Acid. University Chemistry, 2024, 39(9): 369-378. doi: 10.12461/PKU.DXHX202310091
14. [14]
  Xilin Zhao , Xingyu Tu , Zongxuan Li , Rui Dong , Bo Jiang , Zhiwei Miao . Research Progress in Enantioselective Synthesis of Axial Chiral Compounds. University Chemistry, 2024, 39(11): 158-173. doi: 10.12461/PKU.DXHX202403106
15. [15]
  Guangming YIN , Huaiyao WANG , Jianhua ZHENG , Xinyue DONG , Jian LI , Yi'nan SUN , Yiming GAO , Bingbing WANG . Preparation and photocatalytic degradation performance of Ag/protonated g-C₃N₄ nanorod materials. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1491-1500. doi: 10.11862/CJIC.20240086
16. [16]
  Conghao Shi , Ranran Wang , Juli Jiang , Leyong Wang . The Illustration on Stereoisomers of Macrocycles Containing Multiple Chiral Centers via Tröger Base-based Macrocycles. University Chemistry, 2024, 39(7): 394-397. doi: 10.3866/PKU.DXHX202311034
17. [17]
  Zhuo WANG , Junshan ZHANG , Shaoyan YANG , Lingyan ZHOU , Yedi LI , Yuanpei LAN . Preparation and photocatalytic performance of CeO₂-reduced graphene oxide by thermal decomposition. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1708-1718. doi: 10.11862/CJIC.20240067
18. [18]
  Shihui Shi , Haoyu Li , Shaojie Han , Yifan Yao , Siqi Liu . Regioselectively Synthesis of Halogenated Arenes via Self-Assembly and Synergistic Catalysis Strategy. University Chemistry, 2024, 39(5): 336-344. doi: 10.3866/PKU.DXHX202312002
19. [19]
  Heng Chen , Longhui Nie , Kai Xu , Yiqiong Yang , Caihong Fang . 两步焙烧法制备大比表面积和结晶性增强超薄g-C₃N₄纳米片及其高效光催化产H₂O₂. Acta Physico-Chimica Sinica, 2024, 40(11): 2406019-. doi: 10.3866/PKU.WHXB202406019
20. [20]
  Peng YUE , Liyao SHI , Jinglei CUI , Huirong ZHANG , Yanxia GUO . Effects of Ce and Mn promoters on the selective oxidation of ammonia over V₂O₅/TiO₂ catalyst. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 293-307. doi: 10.11862/CJIC.20240210

Get Citation

PDF

XML

Metrics

PDF Downloads(17)
Abstract views(1654)
HTML views(397)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142