Citation: Yuanhong Cai, Donghang Tan, Qiqi Zhang, Wenxin Lv, Qingjiang Li, Honggen Wang. Synthesis of difluoromethylated benzylborons via rhodium(I)-catalyzed fluorine-retainable hydroboration of gem-difluoroalkenes[J]. Chinese Chemical Letters, ;2021, 32(1): 417-420. doi: 10.1016/j.cclet.2020.03.031 shu

Synthesis of difluoromethylated benzylborons via rhodium(I)-catalyzed fluorine-retainable hydroboration of gem-difluoroalkenes

Yuanhong Cai ^a ,
Donghang Tan ^a ,
Qiqi Zhang ^a ,
Wenxin Lv ^a ,
Qingjiang Li ^a ,
Honggen Wang ^{a, b, *,}

a.
Guangdong Provincial Key Laboratory of Chiral Molecule and Drug Discovery, School of Pharmaceutical Sciences, Sun Yat-sen University, Guangzhou 510006, China
b.
State Key Laboratory for Chemistry and Molecular Engineering of Medicinal Resources, School of Chemistry and Pharmaceutical Sciences of Guangxi Normal University, Guilin 541004, China

wanghg3@mail.sysu.edu.cn

Received Date: 9 February 2020
Revised Date: 1 March 2020
Accepted Date: 11 March 2020
Available Online: 13 March 2020

Figures(4)

The synthesis of borylated organofluorines is of great interest due to their potential values as synthons in modular construction of fluorine-containing molecules. Reported herein is a rhodium-catalyzed hydroboration of aryl gem-difluoroalkenes leading to a series of α-difluoromethylated benzylborons. The use of cationic rhodium catalyst and a biphosphine ligand with large bite angle was crucial for reactivity by offering good regioselectivity and diminishing the undesired β-F elimination. Preliminary derivatizations of the products were conducted to showcase the utility of this protocol.
- Rhodium,
- Hydroboration,
- Difluoromethy,
- gem-Difluoroalkene,
- β-F elimination
1. [1]
  (a) K. Muller, C. Faeh, F. Diederich, Science 317 (2007) 1881-1886;
  (b) S. Purser, P.R. Moore, S. Swallow, V. Gouverneur, Chem. Soc. Rev. 37 (2008) 320-330;
  (c) W.K. Hagmann, J. Med. Chem. 51 (2008) 4359-4369;
  (d) J. Wang, M. Sanchez-Rosello, J.L. Acena, et al., Chem. Rev. 114 (2014) 2432-2506.
2. [2]
  (a) J.A. Erickson, J.I. McLoughlin, J. Org. Chem. 60 (1995) 1626-1631;
  (b) N.A. Meanwell, J. Med. Chem. 54 (2011) 2529-2591;
  (c) J. Rong, C. Ni, J. Hu, Asian J. Org. Chem. 6 (2017) 139-152;
  (d) Z. Feng, Y.L. Xiao, X. Zhang, Acc. Chem. Res. 51 (2018) 2264-2278.
3. [3]
  (a) W.J. Middleton, J. Org. Chem. 40 (1975) 574-578;
  (b) J.M. Shreeve, R.P. Singh, Synthesis (2002) 2561-2578;
  (c) P.R. Melvin, D.M. Ferguson, S.D. Schimler, D.C. Bland, M.S. Sanford, Org. Lett. 21 (2019) 1350-1353.
4. [4]
  (a) Z. Feng, Q.Q. Min, X.P. Fu, L. An, X. Zhang, Nat. Commun. 9 (2017) 918-923;
  (b) C. Xu, W.H. Guo, X. He, et al., Nat. Chem. 9 (2018) 1170;
  (c) W. Miao, Y. Zhao, C. Ni, et al., J. Am. Chem. Soc. 140 (2018) 880-883.
5. [5]
  (a) X. Zeng, W. Yan, S.B. Zacate, et al., J. Am. Chem. Soc. 141 (2019) 11398-11403;
  (b) Y. Zhao, W. Huang, J. Zheng, J. Hu, Org. Lett. 13 (2011) 5342-5345;
  (c) P.S. Fier, J.F. Hartwig, J. Am. Chem. Soc. 134 (2012) 5524-5527;
  (d) G.K. Prakash, S.K. Ganesh, J.P. Jones, et al., Angew. Chem. Int. Ed. 51 (2012) 12090-12094;
  (e) J.R. Bour, S.K. Kariofillis, M.S. Sanford, Organometallics 36 (2017) 1220-1223.
6. [6]
  Y. Fujiwara, J.A. Dixon, F. O'Hara, et al., Nature 492 (2012) 95-99. doi: 10.1038/nature11680
7. [7]
  (a) T. Yokomatsu, T. Murano, K. Suemune, S. Shibuya, Tetrahedron 53 (1997) 815-822;
  (b) Q. Xie, Z. Zhu, L. Li, C. Ni, J. Hu, Angew. Chem. Int. Ed. 58 (2019) 6405-6410;
  (c) X. Peng, M.Y. Xiao, J.L. Zeng, F.G. Zhang, J. A. Ma, Org. Lett. 21 (2019) 4808-4811.
8. [8]
  (a) S.V. Kohlhepp, T. Gulder, Chem. Soc. Rev. 45 (2016) 6270-6288;
  (b) N.O. Ilchenko, B.O. Tasch, K.J. Szabo, Angew. Chem. Int. Ed. 53 (2014) 12897-12901;
  (c) F. Scheidt, J. Neufeld, M. Schafer, C. Thiehoff, R. Gilmour, Org. Lett. 20 (2018) 8073-8076;
  (d)T. Kitamura, K. Muta, J. Oyamada, J. Oyamada, J. Org. Chem. 80 (2015) 10431-10436;
  (e) S.M. Banik, J.W. Medley, E.N. Jacobsen, Science 353 (2016) 51-54;
  (f) Z. Zhao, L. Racicot, G.K. Murphy, Angew. Chem. Int. Ed. 56 (2017) 11620-11623.
9. [9]
  W.X. Lv, Q. Li, J.L. Li, et al., Angew. Chem. Int. Ed. 57 (2018) 16544-16548. doi: 10.1002/anie.201810204
10. [10]
  D.H. Tan, E. Lin, W.W. Ji, et al., Adv. Synth. Catal. 360 (2018) 1032-1037. doi: 10.1002/adsc.201701497
11. [11]
  (a) J. Zhang, W. Dai, Q. Liu, S. Cao, Org. Lett. 19 (2017) 3283-3286;
  (b) H. Sakaguchi, Y. Uetake, M. Ohashi, et al., J. Am. Chem. Soc. 139 (2017) 12855-12862;
  (c) H. Sakaguchi, M. Ohashi, S. Ogoshi, Angew. Chem. Int. Ed. 57 (2018) 328-332;
  (d) J. Hu, X. Han, Y. Yuan, Z. Shi, Angew. Chem. Int. Ed. 56 (2017) 13342-13346;
  (e) R. Kojima, K. Kubota, H. Ito, Chem. Commun. 53 (2017) 10688-10691.
12. [12]
  (a) J.K. Jin, W.X. Zheng, H.M. Xia, F.L. Zhang, Y.F. Wang, Org. Lett. 21 (2019) 8414-8418;
  (b) X. Liu, E.E. Lin, G. Chen, et al., Org. Lett. 21 (2019) 8454-8458.
13. [13]
  (a) D. Männig, H. Nöth, Angew. Chem. Int. Ed. 24 (1985) 878-879;
  (b) D.A. Evans, G.C. Fu, A.H. Hoveyda, J. Am. Chem. Soc. 110 (1988) 6917-6918;
  (c) T. Hayashi, Y. Matsumoto, Y. Ito, J. Am. Chem. Soc. 111 (1989) 3426-3428;
  (d) D.R. Edwards, Y.B. Hleba, C.J. Lata, L.A. Calhoun, C.M. Crudden, Angew. Chem. Int. Ed. 46 (2007) 7799-7802;
  (e) J.R. Smith, B.S.L. Collins, M.J. Hesse, et al., J. Am. Chem. Soc. 139 (2017) 9148-9151;
  (f) G.L. Hoang, J.M. Takacs, Chem. Sci. 8 (2017) 4511-4516;
  (g) C.M. Crudden, Y.B. Hleba, A.C. Chen, J. Am. Chem. Soc. 126 (2004) 9200-9201;
  (h) Y. Hu, W. Sun, C. Liu, Synlett 30 (2019) 1105-1110.
14. [14]
  B.M. Trost, L.C. Czabaniuk, Angew. Chem. Int. Ed. 53 (2014) 2826-2851. doi: 10.1002/anie.201305972
15. [15]
  (a) Y. Xi, J.F. Hartwig, J. Am. Chem. Soc. 139 (2017) 12758-12772;
  (b) Y. Cai, X.T. Yang, S.Q. Zhang, et al., Angew. Chem. Int. Ed. 57 (2018) 1376-1380.
16. [16]
  J. Huang, W. Yan, C. Tan, W. Wu, H. Jiang, Chem. Commun. 54 (2018) 1770-1773. doi: 10.1039/C7CC09432A
17. [17]
  (a) S.R. Tamang, D. Bedi, S. Shafiei-Haghighi, et al., Org. Lett. 20 (2018) 6695-6700;
  (b) J. Chen, J. Guo, Z. Lu, Chin. J. Chem. 36 (2018) 1075-1109.
1. [1]
  Kongchuan Wu , Dandan Lu , Jianbin Lin , Ting-Bin Wen , Wei Hao , Kai Tan , Hui-Jun Zhang . Elucidating ligand effects in rhodium(Ⅲ)-catalyzed arene–alkene coupling reactions. Chinese Chemical Letters, 2024, 35(5): 108906-. doi: 10.1016/j.cclet.2023.108906
2. [2]
  Ying-Di Hao , Zhi-Qian Lin , Xiao-Yu Guo , Jiao Liang , Can-Kun Luo , Qian-Tao Wang , Li Guo , Yong Wu . Rhodium-catalyzed Doyle-Kirmse rearrangement reactions of sulfoxoniun ylides. Chinese Chemical Letters, 2024, 35(4): 108834-. doi: 10.1016/j.cclet.2023.108834
3. [3]
  Yi-Fan Wang , Hao-Yun Yu , Hao Xu , Ya-Jie Wang , Xiaodi Yang , Yu-Hui Wang , Ping Tian , Guo-Qiang Lin . Rhodium(Ⅲ)-catalyzed diastereo- and enantioselective hydrosilylation/cyclization reaction of cyclohexadienone-tethered α, β-unsaturated aldehydes. Chinese Chemical Letters, 2024, 35(9): 109520-. doi: 10.1016/j.cclet.2024.109520
4. [4]
  Yujia Shi , Yan Qiao , Pengfei Xie , Miaomiao Tian , Xingwei Li , Junbiao Chang , Bingxian Liu . Rhodium-catalyzed enantioselective in situ C(sp³)−H heteroarylation by a desymmetrization approach. Chinese Chemical Letters, 2024, 35(10): 109544-. doi: 10.1016/j.cclet.2024.109544
5. [5]
  Chuyu Huang , Zhishan Liu , Linping Zhao , Zuxiao Chen , Rongrong Zheng , Xiaona Rao , Yuxuan Wei , Xin Chen , Shiying Li . Metal-coordinated oxidative stress amplifier to suppress tumor growth combined with M2 macrophage elimination. Chinese Chemical Letters, 2024, 35(12): 109696-. doi: 10.1016/j.cclet.2024.109696
6. [6]
  Zengchao Guo , Weiwei Liu , Tengfei Liu , Jinpeng Wang , Hui Jiang , Xiaohui Liu , Yossi Weizmann , Xuemei Wang . Engineered exosome hybrid copper nanoscale antibiotics facilitate simultaneous self-assembly imaging and elimination of intracellular multidrug-resistant superbugs. Chinese Chemical Letters, 2024, 35(7): 109060-. doi: 10.1016/j.cclet.2023.109060
7. [7]
  Yi Zhang , Biao Wang , Chao Hu , Muhammad Humayun , Yaping Huang , Yulin Cao , Mosaad Negem , Yigang Ding , Chundong Wang . Fe–Ni–F electrocatalyst for enhancing reaction kinetics of water oxidation. Chinese Journal of Structural Chemistry, 2024, 43(2): 100243-100243. doi: 10.1016/j.cjsc.2024.100243
8. [8]
  Xinlong WANG , Zhenguo CHENG , Guo WANG , Xiaokuen ZHANG , Yong XIANG , Xinquan WANG . Enhancement of the fragile interface of high voltage LiCoO₂ by surface gradient permeation of trace amounts of Mg/F. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 571-580. doi: 10.11862/CJIC.20230259
9. [9]
  Zhen Liu , Zhi-Yuan Ren , Chen Yang , Xiangyi Shao , Li Chen , Xin Li . Asymmetric alkenylation reaction of benzoxazinones with diarylethylenes catalyzed by B(C₆F₅)₃/chiral phosphoric acid. Chinese Chemical Letters, 2024, 35(5): 108939-. doi: 10.1016/j.cclet.2023.108939
10. [10]
  Dong-Sheng Deng , Su-Qin Tang , Yong-Tu Yuan , Ding-Xiong Xie , Zhi-Yuan Zhu , Yue-Mei Huang , Yun-Lin Liu . C-F insertion reaction sheds new light on the construction of fluorinated compounds. Chinese Chemical Letters, 2024, 35(8): 109417-. doi: 10.1016/j.cclet.2023.109417
11. [11]
  Shuige Zhao , Pengcheng Yan , Peipei Liu , Haishan Liu , Ning Li , Peng Fu , Weiming Zhu . Pyridapeptides F‒I, cyclohexapeptides from marine sponge-derived Streptomyces sp. OUCMDZ-4539. Chinese Chemical Letters, 2024, 35(7): 108950-. doi: 10.1016/j.cclet.2023.108950
12. [12]
  Yu-Yu Tan , Lin-Heng He , Wei-Min He . Copper-mediated assembly of SO₂F group via radical fluorine-atom transfer strategy. Chinese Chemical Letters, 2024, 35(9): 109986-. doi: 10.1016/j.cclet.2024.109986
13. [13]
  Lan Yang , Yu Li , Mou Jiang , Rui Zhou , Hengjiang Cong , Minghui Yang , Lei Zhang , Shenhui Li , Yunhuang Yang , Maili Liu , Xin Zhou , Zhong-Xing Jiang , Shizhen Chen . Fluorinated [2]rotaxanes as sensitive ¹⁹F MRI agents: Threading for higher sensitivity. Chinese Chemical Letters, 2024, 35(10): 109512-. doi: 10.1016/j.cclet.2024.109512
14. [14]
  Yanrui Liu , Paramaguru Ganesan , Peng Gao . Harnessing d-f transition rare earth complexes for single layer white organic light emitting diodes. Chinese Journal of Structural Chemistry, 2024, 43(9): 100369-100369. doi: 10.1016/j.cjsc.2024.100369
15. [15]
  Yang Li , Yihan Chen , Jiaxin Luo , Qihuan Li , Yiwu Quan , Yixiang Cheng . Enhanced circularly polarized luminescence emission promoted by achiral dichroic oligomers of F8BT in cholesteric liquid crystal. Chinese Chemical Letters, 2024, 35(11): 109864-. doi: 10.1016/j.cclet.2024.109864
16. [16]
  Shuai Qiu , Jia He , Xiao Hu , Hongxia Yan , Zhao Gao , Wei Tian . Cation-π enhanced triplet-to-singlet Förster resonance energy transfer for fluorescence afterglow. Chinese Chemical Letters, 2025, 36(4): 110057-. doi: 10.1016/j.cclet.2024.110057
17. [17]
  Xiaoyao Ma , Jinling Zhang , Ge Fang , He Gao , Jie Gao , Li Fu , Yuanyuan Hou , Gang Bai . Förster resonance energy transfer reveals phillygenin and swertiamarin concurrently target AKT on different binding domains to increase the anti-inflammatory effect. Chinese Chemical Letters, 2024, 35(5): 108823-. doi: 10.1016/j.cclet.2023.108823
18. [18]
  Aimin Fu , Chunmei Chen , Qin Li , Nanjin Ding , Jiaxin Dong , Yu Chen , Mengsha Wei , Weiguang Sun , Hucheng Zhu , Yonghui Zhang . Niduenes A−F, six functionalized sesterterpenoids with a pentacyclic 5/5/5/5/6 skeleton from endophytic fungus Aspergillus nidulans. Chinese Chemical Letters, 2024, 35(9): 109100-. doi: 10.1016/j.cclet.2023.109100
19. [19]
  Hui Gu , Mingyue Gao , Kuan Shen , Tianli Zhang , Junhao Zhang , Xiangjun Zheng , Xingmei Guo , Yuanjun Liu , Fu Cao , Hongxing Gu , Qinghong Kong , Shenglin Xiong . F127 assisted fabrication of Ge/rGO/CNTs nanocomposites with three-dimensional network structure for efficient lithium storage. Chinese Chemical Letters, 2024, 35(9): 109273-. doi: 10.1016/j.cclet.2023.109273
20. [20]
  Quanyou Guo , Yue Yang , Tingting Hu , Hongqi Chu , Lijun Liao , Xuepeng Wang , Zhenzi Li , Liping Guo , Wei Zhou . Regulating local electron transfer environment of covalent triazine frameworks through F, N co-modification towards optimized oxygen reduction reaction. Chinese Chemical Letters, 2025, 36(1): 110235-. doi: 10.1016/j.cclet.2024.110235

Get Citation

PDF

XML

Metrics

PDF Downloads(8)
Abstract views(1111)
HTML views(128)

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