Citation: He Zeyu, Fan Min, Xu Jia'neng, Hu Yue, Wang Lu, Wu Xudong, Xia Chungu, Liu Chao. Iron-Catalyzed Deoxygenative Diborylation of Ketones to Internal gem-Diboronates[J]. Chinese Journal of Organic Chemistry, ;2019, 39(12): 3438-3445. doi: 10.6023/cjoc201909008 shu

Iron-Catalyzed Deoxygenative Diborylation of Ketones to Internal gem-Diboronates

He Zeyu ^a,b ,
Fan Min ^a ,
Xu Jia'neng ^a,b ,
Hu Yue ^a ,
Wang Lu ^a ,
Wu Xudong ^a,c ,
Xia Chungu ^a ,
Liu Chao ^a,,

a.
State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences, Lanzhou 730000
b.
University of Chinese Academy of Sciences, Beijing 100049
c.
Department of Chemistry and Chemical Engineering, Yibin University, Yibin, Sichuan 644007

Corresponding author: Liu Chao, chaoliu@licp.cas.cn
Received Date: 6 September 2019
Revised Date: 18 September 2019
Available Online: 25 December 2019
Fund Project: the National Natural Science Foundation of China 21872156the National Natural Science Foundation of China 21673261Project supported by the National Natural Science Foundation of China (Nos. 91745110, 21673261, 21603245, 21633013, 21703265, 21872156, 21802150), the Natural Science Foundation of Jiangsu Province (Nos. BK20181194, BK20180247), the Young Elite Scientist Sponsorship Program by China Association for Science and Technology (No. YESS20170217) and the Youth Innovation Promotion Association of Chinese Academy of Sciences (No. 2018458)the National Natural Science Foundation of China 91745110the National Natural Science Foundation of China 21703265the National Natural Science Foundation of China 21633013the National Natural Science Foundation of China 21802150the Young Elite Scientist Sponsorship Program by China Association for Science and Technology YESS20170217the Natural Science Foundation of Jiangsu Province BK20181194the Youth Innovation Promotion Association of Chinese Academy of Sciences 2018458the National Natural Science Foundation of China 21603245the Natural Science Foundation of Jiangsu Province BK20180247

Figures(4)

An iron catalyzed deoxygenative diborylation of ketones to access a variety of internal gem-diboronates has been developed. A scale-up synthesis of such gem-diboronates is also applicable under this condition. Meanwhile, common organic solvent acetone was used as start material to synthesize corresponding internal gem-diboronate, and further mono- or di-functionalization of such internal gem-diboronate has also been explored to demonstrate the synthetic potential of internal gem-diboronates.
- iron catalysis,
- aliphatic ketone,
- deoxygenative borylation,
- gem-diboronate
1. [1]
  (a) Nallagonda, R.; Padala, K.; Masarwa, A. Org. Biomol. Chem. 2018, 16, 1050.
  (b) Wu, C.; Wang, J. Tetrahedron Lett. 2018, 59, 2128.
  (c) Zhang, Z.-Q.; Yang, C.-T.; Liang, L.-J.; Xiao, B.; Lu, X.; Liu, J.-H.; Sun, Y.-Y.; Marder, T. B.; Fu, Y. Org. Lett. 2014, 16, 6342.
  (d) Zhang, Z.-Q.; Zhang, B.; Lu, X.; Liu, J.-H.; Lu, X.-Y.; Xiao, B.; Fu, Y. Org. Lett. 2016, 18, 952.
  (e) Sun, W.; Wang, L.; Xia, C.; Liu, C. Angew. Chem., Int. Ed. 2018, 57, 5501.
  (f) Brown, H. C.; Rhodes, S. P. J. Am. Chem. Soc. 1969, 91, 4306.
  (g) Coombs, J. R.; Zhang, L.; Morken, J. P. Org. Lett. 2015, 17, 1708.
  (h) Endo, K.; Hirokami, M.; Shibata, T. J. Org. Chem. 2010, 75, 3469.
  (i) Endo, K.; Ohkubo, T.; Hirokami, M.; Shibata, T. J. Am. Chem. Soc. 2010, 132, 11033.
  (j) Endo, K.; Ohkubo, T.; Ishioka, T.; Shibata, T. J. Org. Chem. 2012, 77, 4826.
  (k) Endo, K.; Ohkubo, T.; Shibata, T. Org. Lett. 2011, 13, 3368.
  (l) Hong, K.; Liu, X.; Morken, J. P. J. Am. Chem. Soc. 2014, 136, 10581.
  (m) Jo, W.; Kim, J.; Choi, S.; Cho, S. H. Angew. Chem., Int. Ed. 2016, 55, 9690.
  (n) Kim, J.; Park, S.; Park, J.; Cho, S. H. Angew. Chem., Int. Ed. 2016, 55, 1498.
  (o) Li, H.; Zhang, Z.; Shangguan, X.; Huang, S.; Chen, J.; Zhang, Y.; Wang, J. Angew. Chem., Int. Ed. 2014, 53, 11921.
  (p) Matteson, D. S.; Moody, R. J. J. Am. Chem. Soc. 1977, 99, 3196.
  (q) Matteson, D. S.; Moody, R. J. Organometallics 1982, 1, 20.
  (r) Matteson, D. S.; Moody, R. J.; Jesthi, P. K. J. Am. Chem. Soc. 1975, 97, 5608.
  (s) Park, J.; Lee, Y.; Kim, J.; Cho, S. H. Org. Lett. 2016, 18, 1210.
  (t) Potter, B.; Edelstein, E. K.; Morken, J. P. Org. Lett. 2016, 18, 3286.
  (u) Potter, B.; Szymaniak, A. A.; Edelstein, E. K.; Morken, J. P. J. Am. Chem. Soc. 2014, 136, 17918.
  (v) Sun, C.; Potter, B.; Morken, J. P. J. Am. Chem. Soc. 2014, 136, 6534.
  (w) Xu, S.; Shangguan, X.; Li, H.; Zhang, Y.; Wang, J. J. Org. Chem. 2015, 80, 7779.
  (x) Zhan, M.; Li, R.-Z.; Mou, Z.-D.; Cao, C.-G.; Liu, J.; Chen, Y.-W.; Niu, D. ACS Catal. 2016, 6, 3381.
  (y) Iacono, C. E.; Stephens, T. C.; Rajan, T. S.; Pattison, G. J. Am. Chem. Soc. 2018, 140, 2036.
  (z) Kim, J.; Shin, M.; Cho, S. H. ACS Catal. 2019, 8503.
  (aa) Kim, J.; Lee, E.; Cho, S. H. Asian J. Org. Chem. 2019, 8, 1664.
  (ab) Lee, H.; Lee, Y.; Cho, S. H. Org. Lett. 2019, 21, 5912.
  (ac) Kim, J.; Hwang, C.; Kim, Y.; Cho, S. H. Org. Process Res. Dev. 2019, 23, 1663.
  (ad) Kim, J.; Cho, S. H. ACS Catal. 2019, 9, 230.
  (ae) Park, J.; Choi, S.; Lee, Y.; Cho, S. H. Org. Lett. 2017, 19, 4054.
  (af) Kim, J.; Ko, K.; Cho, S. H. Angew. Chem., Int. Ed. 2017, 56, 11584.
  (ag) Lee, Y.; Park, J.; Cho, S. H. Angew. Chem., Int. Ed. 2018, 57, 12930.
2. [2]
  (a) Zheng, P.; Zhai, Y.; Zhao, X.; Xu, T. Chem. Commun. 2018, 54, 13375.
  (b) Zheng, P.; Zhai, Y.; Zhao, X.; Xu, T. Org. Lett. 2019, 21, 393.
3. [3]
  (a) Zhao, H.; Tong, M.; Wang, H.; Xu, S. Org. Biomol. Chem. 2017, 15, 3418.
  (b) Hwang, C.; Jo, W.; Cho, S. H. Chem. Commun. 2017, 53, 7573.
  (c) Liu, X.; Deaton, T. M.; Haeffner, F.; Morken, J. P. Angew. Chem., Int. Ed. 2017, 56, 11485.
4. [4]
  (a) Harris, M. R.; Wisniewska, H. M.; Jiao, W.; Wang, X.; Bradow, J. N. Org. Lett. 2018, 20, 2867.
  (b) Sandford, C.; Aggarwal, V. K. Chem. Commun. 2017, 53, 5481.
  (c) Liu, Y.; Zhang, W. Chin. J. Org. Chem. 2016, 36, 2249 (in Chinese).
  (刘媛媛, 张万斌, 有机化学, 2016, 36, 2249.)
  (d) Chen, D.; Xu, M.-H. Chin. J. Org. Chem. 2017, 37, 1589 (in Chinese).
  (陈雕, 徐明华, 有机化学, 2017, 37, 1589.)
  (e) Xu, X.; Cheng, R.; Qiu, Z.; Pan, C. Chin. J. Org. Chem. 2018, 38, 3078 (in Chinese).
  (许新彬, 程若飞, 邱早早, 潘成岭, 有机化学, 2018, 38, 3078.)
5. [5]
  Li, Z.; Wang, Z.; Zhu, L.; Tan, X.; Li, C. J. Am. Chem. Soc. 2014, 136, 16439. doi: 10.1021/ja509548z
6. [6]
  Masaki, S.; Michael, S.; Ikuhiro, N.; Katsuhiro, S.; Takuya, K.; Tamejiro, H. Chem. Lett. 2006, 35, 1222. doi: 10.1246/cl.2006.1222
7. [7]
  (a) Edelstein, E. K.; Grote, A. C.; Palkowitz, M. D.; Morken, J. P. Synlett 2018, 29, 1749.
  (b) Li, X.; Hall, D. G. Angew. Chem., Int. Ed. 2018, 57, 10304.
8. [8]
  (a) Palmer, W. N.; Zarate, C.; Chirik, P. J. J. Am. Chem. Soc. 2017, 139, 2589.
  (b) Zhang, L.; Huang, Z. J. Am. Chem. Soc. 2015, 137, 15600.
9. [9]
  (a) Brown, H. C.; Scouten, C. G.; Liotta, R. J. Am. Chem. Soc. 1979, 101, 96.
  (b) Espinal-Viguri, M.; Woof, C. R.; Webster, R. L. Chem.-Eur. J. 2016, 22, 11605.
  (c) He, T.; Li, B.; Liu, L.-C.; Wang, J.; Ma, W.-P.; Li, G.-Y.; Zhang, Q.-W.; He, W. Chem.-Eur. J. 2019, 25, 966.
  (d) Yukimori, D.; Nagashima, Y.; Wang, C.; Muranaka, A.; Uchiyama, M. J. Am. Chem. Soc. 2019, 141, 9819.
  (e) Yuma, N.; Naofumi, T. Lett. Org. Chem. 2017, 14, 243.
10. [10]
  Lee, S.; Li, D.; Yun, J. Chem.-Asian J. 2014, 9, 2440. doi: 10.1002/asia.201402458
11. [11]
  (a) Li, H.; Shangguan, X.; Zhang, Z.; Huang, S.; Zhang, Y.; Wang, J. Org. Lett. 2014, 16, 448.
  (b) Cuenca, A. B.; Cid, J.; García-López, D.; Carbó, J. J.; Fernández, E. Org. Biomol. Chem. 2015, 13, 9659.
12. [12]
  (a) Abu Ali, H.; Goldberg, I.; Kaufmann, D.; Burmeister, C.; Srebnik, M. Organometallics 2002, 21, 1870.
  (b) Wommack, A. J.; Kingsbury, J. S. Tetrahedron Lett. 2014, 55, 3163.
13. [13]
  Wang, L.; Zhang, T.; Sun, W.; He, Z.; Xia, C.; Lan, Y.; Liu, C. J. Am. Chem. Soc. 2017, 139, 5257. doi: 10.1021/jacs.7b02518
14. [14]
  He, Z.; Zhu, Q.; Hu, X.; Wang, L.; Xia, C.; Liu, C. Org. Chem. Front. 2019, 6, 900. doi: 10.1039/C9QO00007K
15. [15]
  Bonet, A.; Odachowski, M.; Leonori, D.; Essafi, S.; Aggarwal, V. K. Nat. Chem. 2014, 6, 584. doi: 10.1038/nchem.1971
16. [16]
  (a) Bedford, R. B.; Brenner, P. B.; Carter, E.; Gallagher, T.; Murphy, D. M.; Pye, D. R. Organometallics 2014, 33, 5940.
  (b) Laitar, D. S.; Tsui, E. Y.; Sadighi, J. P. J. Am. Chem. Soc. 2006, 128, 11036.
  (c) Nakagawa, N.; Hatakeyama, T.; Nakamura, M. Chem.-Eur. J. 2015, 21, 4257.
  (d) Zhao, H.; Dang, L.; Marder, T. B.; Lin, Z. J. Am. Chem. Soc. 2008, 130, 5586.
  (e) Zhou, Y.; Wang, H.; Liu, Y.; Zhao, Y.; Zhang, C.; Qu, J. Org. Chem. Front. 2017, 4, 1580.
1. [1]
  Shuai Tang , Zian Wang , Mengyi Zhu , Xinyun Zhao , Xiaoyun Hu , Hua Zhang . Synthesis of organoboron compounds via heterogeneous C–H and C–X borylation. Chinese Chemical Letters, 2025, 36(5): 110503-. doi: 10.1016/j.cclet.2024.110503
2. [2]
  Mengyu Wu , Kewei Ren , Chengyu Zou , Jiacheng Chen , Rui Ma , Chuan Zhu , Chao Feng . A general synthesis of gem–difluorobicyclo[2.1.1]hexanes. Chinese Chemical Letters, 2025, 36(5): 110213-. doi: 10.1016/j.cclet.2024.110213
3. [3]
  Wen-Tao Ouyang , Jun Jiang , Yan-Fang Jiang , Ting Li , Yuan-Yuan Liu , Hong-Tao Ji , Li-Juan Ou , Wei-Min He . Sono-photocatalytic amination of quinoxalin-2(1H)-ones with aliphatic amines. Chinese Chemical Letters, 2024, 35(10): 110038-. doi: 10.1016/j.cclet.2024.110038
4. [4]
  Conghui Wang , Lei Xu , Zhenhua Jia , Teck-Peng Loh . Recent applications of macrocycles in supramolecular catalysis. Chinese Chemical Letters, 2024, 35(4): 109075-. doi: 10.1016/j.cclet.2023.109075
5. [5]
  Wei Chen , Pieter Cnudde . A minireview to ketene chemistry in zeolite catalysis. Chinese Journal of Structural Chemistry, 2024, 43(11): 100412-100412. doi: 10.1016/j.cjsc.2024.100412
6. [6]
  Lin Zhang , Chaoran Li , Thongthai Witoon , Xingda An , Le He . Nano-thermometry in photothermal catalysis. Chinese Journal of Structural Chemistry, 2025, 44(4): 100456-100456. doi: 10.1016/j.cjsc.2024.100456
7. [7]
  Yi ZHANG , Guang LI , Wenxuan FAN , Qingfeng YI . Influence of bismuth trisulfide on the electrochemical performance of iron electrode. Chinese Journal of Inorganic Chemistry, 2025, 41(6): 1196-1206. doi: 10.11862/CJIC.20240445
8. [8]
  Yu Mao , Yilin Liu , Xiaochen Wang , Shengyang Ni , Yi Pan , Yi Wang . Acylfluorination of enynes via phosphine and silver catalysis. Chinese Chemical Letters, 2024, 35(8): 109443-. doi: 10.1016/j.cclet.2023.109443
9. [9]
  Jiaqi Jia , Kathiravan Murugesan , Chen Zhu , Huifeng Yue , Shao-Chi Lee , Magnus Rueping . Multiphoton photoredox catalysis enables selective hydrodefluorinations. Chinese Chemical Letters, 2025, 36(2): 109866-. doi: 10.1016/j.cclet.2024.109866
10. [10]
  Peng Wang , Jianjun Wang , Ni Song , Xin Zhou , Ming Li . Radical dehydroxymethylative fluorination of aliphatic primary alcohols and diverse functionalization of α-fluoroimides via BF₃·OEt₂-catalyzed C‒F bond activation. Chinese Chemical Letters, 2025, 36(1): 109748-. doi: 10.1016/j.cclet.2024.109748
11. [11]
  Zhongsen Wang , Lijun Qiu , Yunhua Huang , Meng Zhang , Xi Cai , Fanyu Wang , Yang Lin , Yanbiao Shi , Xiao Liu . Alcohothermal synthesis of sulfidated zero-valent iron for enhanced Cr(Ⅵ) removal. Chinese Chemical Letters, 2024, 35(7): 109195-. doi: 10.1016/j.cclet.2023.109195
12. [12]
  Jiangshan Xu , Weifei Zhang , Zhengwen Cai , Yong Li , Long Bai , Shaojingya Gao , Qiang Sun , Yunfeng Lin . Tetrahedron DNA nanostructure/iron-based nanomaterials for combined tumor therapy. Chinese Chemical Letters, 2024, 35(11): 109620-. doi: 10.1016/j.cclet.2024.109620
13. [13]
  Xianzheng Zhang , Yana Chen , Zhiyong Ye , Huilin Hu , Ling Lei , Feng You , Junlong Yao , Huan Yang , Xueliang Jiang . Magnetic field-assisted microbial corrosion construction iron sulfides incorporated nickel-iron hydroxide towards efficient oxygen evolution. Chinese Journal of Structural Chemistry, 2024, 43(1): 100200-100200. doi: 10.1016/j.cjsc.2023.100200
14. [14]
  Jiyang Liu , Xiangzhang Tao , Zhenlei Zou , Jia Xu , Hui Shu , Yi Pan , Weigang Zhang , Shengyang Ni , Yi Wang . Modular and practical synthesis of gem-difluoroalkenes via consecutive Ni-catalyzed reductive cross-coupling. Chinese Chemical Letters, 2025, 36(7): 110461-. doi: 10.1016/j.cclet.2024.110461
15. [15]
  Ning LI , Siyu DU , Xueyi WANG , Hui YANG , Tao ZHOU , Zhimin GUAN , Peng FEI , Hongfang MA , Shang JIANG . Preparation and efficient catalysis for olefins epoxidation of a polyoxovanadate-based hybrid. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 799-808. doi: 10.11862/CJIC.20230372
16. [16]
  Uttam Pandurang Patil . Porous carbon catalysis in sustainable synthesis of functional heterocycles: An overview. Chinese Chemical Letters, 2024, 35(8): 109472-. doi: 10.1016/j.cclet.2023.109472
17. [17]
  Liliang Chu , Xiaoyan Zhang , Jianing Li , Xuelei Deng , Miao Wu , Ya Cheng , Weiping Zhu , Xuhong Qian , Yunpeng Bai . Continuous-flow synthesis of polysubstituted γ-butyrolactones via enzymatic cascade catalysis. Chinese Chemical Letters, 2024, 35(4): 108896-. doi: 10.1016/j.cclet.2023.108896
18. [18]
  Hao-Cong Li , Ming Zhang , Qiyan Lv , Kai Sun , Xiao-Lan Chen , Lingbo Qu , Bing Yu . Homogeneous catalysis and heterogeneous separation: Ionic liquids as recyclable photocatalysts for hydroacylation of olefins. Chinese Chemical Letters, 2025, 36(2): 110579-. doi: 10.1016/j.cclet.2024.110579
19. [19]
  Jing Guo , Jianzhong Ma , Junli Liu , Guanjie Huang , Xiaoting Zhou , Francesco Parrino , Riccardo Ceccato , Leonardo Palmisano , Boon-Junn Ng , Lutfi Kurnianditia Putri , Huaxing Li , Rongjie Li , Gang Liu , Yang Wang , Nikolay Kornienko , Shan-Shan Zhu , Zhenwei Zhang , Xiaoming Liu , Nur Atika Nikma Dahlan , Siang-Piao Chai , Jianmin Ma . Two-dimensional nanomaterials for environmental catalysis roadmap towards 2030. Chinese Chemical Letters, 2025, 36(9): 110988-. doi: 10.1016/j.cclet.2025.110988
20. [20]
  Xing Tian , Di Wu , Wanheng Wei , Guifu Dai , Zhanxian Li , Benhua Wang , Mingming Yu . A lipid droplets-targetable fluorescent probe for polarity detection in cells of iron death, inflammation and fatty liver tissue. Chinese Chemical Letters, 2024, 35(6): 108912-. doi: 10.1016/j.cclet.2023.108912

Get Citation

PDF

XML

Metrics

PDF Downloads(10)
Abstract views(804)
HTML views(67)

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