Citation: Wang Qiaotian, Han Caifang, Feng Xiangqing, Du Haifeng. Chiral Spiro Dienes Derived Boranes for Asymmetric Hydrosilylation of Ketones[J]. Chinese Journal of Organic Chemistry, ;2019, 39(8): 2257-2263. doi: 10.6023/cjoc201903076 shu

Chiral Spiro Dienes Derived Boranes for Asymmetric Hydrosilylation of Ketones

Wang Qiaotian ^a,b ,
Han Caifang ^a,b ,
Feng Xiangqing ^a,b,, ,
Du Haifeng ^a,b,,

a.
Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190
b.
University of Chinese Academy of Sciences, Beijing 100049

Corresponding author: Feng Xiangqing, fxq@iccas.ac.cn Du Haifeng, haifengdu@iccas.ac.cn
Received Date: 30 March 2019
Revised Date: 24 April 2019
Available Online: 10 August 2019
Fund Project: the National Natural Science Foundation of China 21825108Project supported by the National Natural Science Foundation of China (No. 21825108)

Figures(5)

The chemistry of frustrated Lewis pairs (FLPs) is among the challenging frontiers of synthetic chemistry, which provides a powerful approach for metal-free catalytic hyrogenations and Piers-type hydrosilylations. In recent years, a significant progress has been made in this field. However, the deveopment of asymmetric reactions is still sluggish. The lacks of highly effective and enantioselective chiral FLP catalysts represent the key issue. C₂-symmetric 1, 1'-spirobiindane is one privileged framework in chiral ligands and catalysts. On the basis of chiral binaphthyl diene-derived frustrated Lewis pairs (FLPs) developed by our group, in this work, we designed and synthesized a novel class of chiral spiro dienes, which could further react with Piers' borane via the hydroboration reaction to generate chiral boranes in situ. With the combination of chiral borane and tri-tert-butylphosphine as an FLP catalyst, an asymmetric Piers-type hydrosilylation of simple ketones was successfully realized to give the desired secondary alcohols with up to 90% ee.
- asymmetric catalysis,
- asymmetric hydrosilylation,
- frustrated Lewis pairs,
- chiral spiro dienes,
- ketones
1. [1]
  Welch, G. C.; San Juan, R. R.; Masuda, J. D.; Stephan, D. W. Science 2006, 314, 1124. doi: 10.1126/science.1134230
2. [2]
  (a) Stephan, D. W. Org. Biomol. Chem. 2008, 6, 1535.
  (b) Kenward, A. L.; Piers, W. E. Angew. Chem., Int. Ed. 2008, 47, 38.
  (c) Stephan, D. W.; Erker, G. Angew. Chem., Int. Ed. 2010, 49, 46.
  (d) Soös, T. Pure Appl. Chem. 2011, 83, 667.
  (e) Erker, G. Pure Appl. Chem. 2012, 84, 2203.
  (f) Stephan, D. W. Org. Biomol. Chem. 2012, 10, 5740.
  (g) Paradies, J. Angew. Chem., Int. Ed. 2014, 53, 3552.
  (h) Stephan, D. W. Acc. Chem. Res. 2015, 48, 306.
  (i) Stephan, D. W.; Erker, G. Angew. Chem., Int. Ed. 2015, 54, 6400.
  (j) Oestreich, M.; Hermeke, J.; Mohr, J. Chem. Soc. Rev. 2015, 44, 2202.
  (k) Stephan, D. W. Science 2016, 354, aaf7229.
3. [3]
  (a) Liu, Y.; Du, H. Acta Chim. Sinica 2014, 72, 771(in Chinese).
  (刘勇兵, 杜海峰, 化学学报, 2014, 72, 771.)
  (b) Feng, X.; Du, H. Tetrahedron Lett. 2014, 55, 6959.
  (c) Shi, L.; Zhou, Y.-G. ChemCatChem 2015, 7, 54.
  (d) Meng, W.; Feng, X.; Du, H. Acc. Chem. Res. 2018, 51, 191.
4. [4]
  (a) Sumerin, V.; Chernichenko, K.; Nieger, M.; Leskelä, M.; Rieger, B.; Repo, T. Adv. Synth. Catal. 2011, 353, 2093.
  (b) Mewald, M.; Fröhlich, R.; Oestreich, M. Chem.-Eur. J. 2011, 17, 9406.
  (c) Mewald, M.; Oestreich, M. Chem.-Eur. J. 2012, 18, 14079.
  (d) Lindqvist, M.; Borre, K.; Axenov, K.; Kótai, B.; Nieger, M.; Leskelä, M.; Pápai, I.; Repo, T. J. Am. Chem. Soc. 2015, 137, 4038.
  (e) Süsse, L.; Hermeke, J.; Oestreich, M. J. Am. Chem. Soc. 2016, 138, 6940.
  (f) Lam, J.; Günther, B. A. R.; Farrell, J. M.; Eisenberger, P.; Bestvater, B. P.; Newman, P. D.; Melen, R. L.; Crudden, C. M.; Stephan, D. W. Dalton Trans. 2016, 45, 15303.
5. [5]
  (a) Chen, D.; Wang, Y.; Klankermayer, J. Angew. Chem., Int. Ed. 2010, 49, 9475.
  (b) Chen, D.; Leich, V.; Pan, F.; Klankermayer, J. Chem.-Eur. J. 2012, 18, 5184.
  (c) Ghattas, G.; Chen, D.; Pan, F.; Klankermayer, J. Dalton Trans. 2012, 41, 9026.
  (d) Ye, K.-Y.; Wang, X.; Daniliuc, C. G.; Kehr, G.; Erker, G. Eur. J. Inorg. Chem. 2017, 368.
  (e) Chen, D.; Klankermayer, J. Chem. Commun. 2008, 2130.
6. [6]
  (a) Parks, D. J.; Spence, R. E. von H.; Piers, W. E. Angew. Chem., Int. Ed. 1995, 34, 809.
  (b) Parks, D. J.; Piers, W. E.; Yap, G. P. A. Organometallics 1998, 17, 5492.
7. [7]
  (a) Liu, Y.; Du, H. J. Am. Chem. Soc. 2013, 135, 12968.
  (b) Wei, S.; Du, H. J. Am. Chem. Soc. 2014, 136, 12261.
  (c) Zhang, Z.; Du, H. Angew. Chem., Int. Ed. 2015, 54, 623.
  (d) Ren, X.; Du, H. J. Am. Chem. Soc. 2016, 138, 810.
  (e) Liu, X.; Wang, Q.; Han, C.; Feng, X.; Du, H. Chin. J. Chem. 2019, 37, 663.
8. [8]
  (a) Tu, X.-S.; Zeng, N.-N.; Li, R.-Y.; Zhao, Y.-Q.; Xie, D.-Z.; Peng Q.; Wang, X.-C. Angew. Chem., Int. Ed. 2018, 57, 15096.
  (b) Li, X.; Tian, J.-J.; Liu, N.; Tu, X.-S.; Zeng, N.-N.; Wang, X.-C. Angew. Chem., Int. Ed. 2019, 58, 4664.
9. [9]
  Zhou, Q.-L., Privileged Chiral Ligands and Catalysts, Wiley-VCH, Weinheim, Germany, 2011.
10. [10]
  For selected reviews, see: (a) Xie, J.-H.; Zhou, Q.-L. Acc. Chem. Res. 2008, 41, 581.
  (b) Ding, K.-L.; Han, Z.-B.; Wang, Z. Chem. Asian J. 2009, 4, 32.
  (c) Xie, J.-H.; Zhou, Q.-L. Acta Chim. Sinica 2014, 72, 778(in Chinese).
  (谢建华, 周其林, 化学学报, 2014, 72, 778.)
  (d) Xie, J.-H.; Bao, D.-H.; Zhou, Q.-L. Synthesis 2015, 47, 460.
  (d) Zhu, S.-F.; Zhou, Q.-L. Acc. Chem. Res. 2012, 45, 1365.
11. [11]
  For a pioneering work, see: Parks, D. J.; Piers, W. E. J. Am. Chem. Soc. 1996, 118, 9440.
12. [12]
  Rendler, S.; Oestreich, M. Angew. Chem., Int. Ed. 2008, 47, 5997. doi: 10.1002/anie.200801675
13. [13]
  Zhu, S.-F.; Yang, Y.; Wang, L.-X.; Liu, B.; Zhou, Q.-L. Org. Lett. 2005, 7, 2333. doi: 10.1021/ol050556x
14. [14]
  Zheng, J.; Cui, W.-J.; Zheng, C.; You, S.-L. J. Am. Chem. Soc. 2016, 138, 5242. doi: 10.1021/jacs.6b02302
15. [15]
  For details, see the Supporting Information. CCDC 1905630 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
16. [16]
  (a) Sokeirik, Y. S.; Mori, H.; Omote, M; Sato, K.; Tarui, A.; Kumadaki, I.; Ando, A. Org. Lett. 2007, 9, 1927.
  (b) Wu, W.; Liu, S.; Duan, M.; Tan, X.; Chen, C.; Xie, Y.; Lan, Y.; Dong, X.; Zhang, X. Org. Lett. 2016, 18, 2938.
  (c) Ren, X.; Li, G.; Wei, S.; Du, H. Org. Lett. 2015, 17, 990.
  (d) Zhang, Z.; Jain, P.; Antilla, J. C. Angew. Chem., Int. Ed. 2011, 50, 10961.
  (e) Süsse, L.; Hermeke, J.; Oestreich, M. J. Am. Chem. Soc. 2016, 138, 6940.
  (f) Chen, X.; Lu, Z. Org. Lett. 2016, 18, 4658.
1. [1]
  Long Jin , Jian Han , Dongmei Fang , Min Wang , Jian Liao . Pd-catalyzed asymmetric carbonyl alkynylation: Synthesis of axial chiral ynones. Chinese Chemical Letters, 2024, 35(6): 109212-. doi: 10.1016/j.cclet.2023.109212
2. [2]
  Jieshuai Xiao , Yuan Zheng , Yue Zhao , Zhuangzhi Shi , Minyan Wang . Asymmetric Nozaki-Hiyama-Kishi (NHK)-type reaction of isatins with aromatic iodides by cobalt catalysis. Chinese Chemical Letters, 2025, 36(5): 110243-. doi: 10.1016/j.cclet.2024.110243
3. [3]
  Mianfeng Li , Haozhi Wang , Zijun Yang , Zexiang Yin , Yuan Liu , Yingmei Bian , Yang Wang , Xuerong Zheng , Yida Deng . Synergistic enhancement of alkaline hydrogen evolution reaction by role of Ni-Fe LDH introducing frustrated Lewis pairs via vacancy-engineered. Chinese Chemical Letters, 2025, 36(3): 110199-. doi: 10.1016/j.cclet.2024.110199
4. [4]
  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
5. [5]
  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
6. [6]
  Ruixue Liu , Xiaobing Ding , Qiwei Lang , Gen-Qiang Chen , Xumu Zhang . Enantioselective and divergent construction of chiral amino alcohols and oxazolidin-2-ones via Ir-f-phamidol-catalyzed dynamic kinetic asymmetric hydrogenation. Chinese Chemical Letters, 2025, 36(3): 110037-. doi: 10.1016/j.cclet.2024.110037
7. [7]
  Pei Cao , Yilan Wang , Lejian Yu , Miao Wang , Liming Zhao , Xu Hou . Dynamic asymmetric mechanical responsive carbon nanotube fiber for ionic logic gate. Chinese Chemical Letters, 2024, 35(6): 109421-. doi: 10.1016/j.cclet.2023.109421
8. [8]
  Yanxin Jiang , Kwai Wun Cheng , Zhiping Yang , Jun (Joelle) Wang . Pd-catalyzed enantioselective and regioselective asymmetric hydrophosphorylation and hydrophosphinylation of enynes. Chinese Chemical Letters, 2025, 36(5): 110231-. doi: 10.1016/j.cclet.2024.110231
9. [9]
  Yu-Hang Miao , Zheng-Xu Zhang , Xu-Yi Huang , Yuan-Zhao Hua , Shi-Kun Jia , Xiao Xiao , Min-Can Wang , Li-Ping Xu , Guang-Jian Mei . Catalytic asymmetric dearomative azo-Diels–Alder reaction of 2-vinlyindoles. Chinese Chemical Letters, 2024, 35(4): 108830-. doi: 10.1016/j.cclet.2023.108830
10. [10]
  Chao Chen , Wenwen Yu , Guangen Huang , Xuelian Ren , Xiangli Chen , Yixin Li , Shenggui Liang , Mengmeng Xu , Mingyue Zheng , Yaxi Yang , He Huang , Wei Tang , Bing Zhou . Asymmetric macrocyclization enabled by Rh(Ⅲ)-catalyzed CH activation: Enantioenriched macrocyclic inhibitor of Zika virus infection. Chinese Chemical Letters, 2024, 35(11): 109574-. doi: 10.1016/j.cclet.2024.109574
11. [11]
  Xiang Huang , Dongzhen Xu , Yang Liu , Xia Huang , Yangfan Wu , Dongmei Fang , Bing Xia , Wei Jiao , Jian Liao , Min Wang . Asymmetric synthesis of difluorinated α-quaternary amino acids (DFAAs) via Cu-catalyzed difluorobenzylation of aldimine esters. Chinese Chemical Letters, 2024, 35(12): 109665-. doi: 10.1016/j.cclet.2024.109665
12. [12]
  Guang Xu , Cuiju Zhu , Xiang Li , Kexin Zhu , Hao Xu . Copper-catalyzed asymmetric [4+1] annulation of yne–allylic esters with pyrazolones. Chinese Chemical Letters, 2025, 36(4): 110114-. doi: 10.1016/j.cclet.2024.110114
13. [13]
  Ming Huang , Xiuju Cai , Yan Liu , Zhuofeng Ke . Base-controlled NHC-Ru-catalyzed transfer hydrogenation and α-methylation/transfer hydrogenation of ketones using methanol. Chinese Chemical Letters, 2024, 35(7): 109323-. doi: 10.1016/j.cclet.2023.109323
14. [14]
  Zhirong Yang , Shan Wang , Ming Jiang , Gengchen Li , Long Li , Fangzhi Peng , Zhihui Shao . One stone three birds: Ni-catalyzed asymmetric allenylic substitution of allenic ethers, hydroalkylation of 1,3-enynes and double alkylation of enynyl ethers. Chinese Chemical Letters, 2024, 35(8): 109518-. doi: 10.1016/j.cclet.2024.109518
15. [15]
  Xiaohui Fu , Yanping Zhang , Juan Liao , Zhen-Hua Wang , Yong You , Jian-Qiang Zhao , Mingqiang Zhou , Wei-Cheng Yuan . Palladium-catalyzed enantioselective decarboxylation of vinyl cyclic carbamates: Generation of amide-based aza-1,3-dipoles and application to asymmetric 1,3-dipolar cycloaddition. Chinese Chemical Letters, 2024, 35(12): 109688-. doi: 10.1016/j.cclet.2024.109688
16. [16]
  Jingyu Chen , Sha Wu , Yuhao Wang , Jiong Zhou . Near-perfect separation of alicyclic ketones and alicyclic alcohols by nonporous adaptive crystals of perethylated pillar[5]arene and pillar[6]arene. Chinese Chemical Letters, 2025, 36(4): 110102-. doi: 10.1016/j.cclet.2024.110102
17. [17]
  Ke Zhang , Sheng Zuo , Pengyuan You , Tong Ru , Fen-Er Chen . Palladium-catalyzed stereoselective decarboxylative [4 + 2] cyclization of 2-methylidenetrimethylene carbonates with pyrrolidone-derived enones: Straightforward access to chiral tetrahydropyran-fused spiro-pyrrolidine-2,3-diones. Chinese Chemical Letters, 2024, 35(6): 109157-. doi: 10.1016/j.cclet.2023.109157
18. [18]
  Heng Yang , Zhijie Zhou , Conghui Tang , Feng Chen . Recent advances in heterogeneous hydrosilylation of unsaturated carbon-carbon bonds. Chinese Chemical Letters, 2024, 35(6): 109257-. doi: 10.1016/j.cclet.2023.109257
19. [19]
  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
20. [20]
  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

Get Citation

PDF

XML

Metrics

PDF Downloads(5)
Abstract views(978)
HTML views(182)

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