Citation: Li Maolin, Chen Mengqing, Xu Bin, Zhu Shoufei, Zhou Qilin. Enantioselective O-H Bond Insertion of α-Diazoketones with Alcohols Cooperatively Catalyzed by Achiral Dirhodium Complexes and Chiral Spiro Phosphoric Acids[J]. Acta Chimica Sinica, ;2018, 76(11): 883-889. doi: 10.6023/A18060234 shu

Enantioselective O-H Bond Insertion of α-Diazoketones with Alcohols Cooperatively Catalyzed by Achiral Dirhodium Complexes and Chiral Spiro Phosphoric Acids

Li Maolin ^a,† ,
Chen Mengqing ^a,† ,
Xu Bin ^a ,
Zhu Shoufei ^a,, ,
Zhou Qilin ^a,b,,

a.
State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071
b.
Collaborative Innovation Center of Chemical Science and Engineering, Tianjin 300072

Corresponding author: Zhu Shoufei, sfzhu@nankai.edu.cn Zhou Qilin, qlzhou@nankai.edu.cn

^†

Supporting information

http://sioc-journal.cn

Received Date: 15 June 2018
Available Online: 14 November 2018
Fund Project: the National Natural Science Foundation of China 21532003the National Natural Science Foundation of China 21421062the "111" Project of the Ministry of Education of China B06005Project supported by the National Natural Science Foundation of China (Nos. 21625204, 21532003, 21421062), the "111" Project of the Ministry of Education of China (No. B06005), the National Program for Special Support of Eminent Professionals and the Fundamental Research Funds for the Central Universitiesthe National Natural Science Foundation of China 21625204

Figures(3)

Transition-metal-catalyzed asymmetric insertion of carbene into O-H bonds is a straightforward method for the synthesis of chiral alcohols and their derivatives. In recent years, a variety of chiral catalysts have been developed to achieve high enantioselective insertions of metal carbenes derived from α-diazoesters into O-H bonds of alcohols, phenols, carboxylic acids, and even water. However, there are few successful examples of the asymmetric O-H bond insertion using α-diazoketones as carbene precursors. In this paper, we report the first asymmetric O-H insertion of α-diazoketones with alcohols co-catalyzed by achiral dirhodium complexes and chiral spiro phosphoric acids. The reaction has high yields and high enantioselectivity (up to 95% ee). The present O-H bond insertion reaction provides an efficient method for the synthesis of very useful chiral α-alkoxy ketones, which are easily transformed to corresponding 1, 2-diol derivatives with excellent diastereoselectivity. The density functional theory (DFT) calculation was performed to study the mechanism of the reaction. It is found that the chiral spiro phosphoric acid can promote the proton transfer process of enol intermediates generated from rhodium carbene and alcohol like chiral proton-transfer shuttle and realize enantioselectivity control accordingly. Water are likely to participate in this proton transfer step and has a remarkable effect on the enantiocontrol of the reaction. A typical procedure for the enantioselective O-H bond insertion of α-diazoketones is as follows. Powered Rh₂(TPA)₄ (2.9 mg, 0.002 mmol, 1 mol%) and chiral spiro phosphoric acid (R)-1k (3.3 mg, 0.004 mmol, 2 mol%) were introduced into an oven-dried Schlenk tube in an argon-filled glovebox. After CHCl₃ (2 mL) was injected into the Schlenk tube, the solution was stirred at 25℃ under the argon atmosphere. A solution of benzyl alcohol (21.6 mg, 0.2 mmol) and 1-diazo-1-phenylpropan-2-one (2a, 33.8 mg, 0.21 mmol) in 1 mL of CHCl₃ were then introduced into the Schlenk tube containing catalysts. The resulting mixture was stirred at 25℃ until the diazo compound 2a disappeared. After concentration in vacuo, the residue was purified by flash chromatography on silica gel (petroleum ether/ethyl acetate, V:V=15:1) to give (-)-1-(benzyloxy)-1-phenyl-propan-2-one (4a, 43.2 mg, 0.18 mmol, 90% yield) as a colorless oil.
- metal carbene,
- asymmetric insertion reaction,
- chiral spiro phosphoric acid,
- α-diazoketone,
- chiral α-alkoxy ketone
1. [1]
2. [2]
  For selected reviews, see: (a) Ye, T.; Mckervey, M. A. Chem.Rev. 1994, 94, 1091. (b) Zhang, Z.-H.; Wang, J.-B. Tetrahedron 2008, 64, 6577. (c) Zhu, S.-F.; Zhou, Q.-L. Acc.Chem.Res. 2012, 45, 1365. (d) Fei, N.; Gillingham, D. Chem.Soc.Rev. 2013, 42, 4918. (e) Zhu, S.-F.; Zhou, Q.-L. Nat.Sci.Rev. 2014, 1, 580. (f) Maguire, A. R.; McKervey, M. A. Chem.Rev. 2015, 115, 9981.
3. [3]
  For selected examples, see: (a) Maier, T. C.; Fu, G. C. J.Am.Chem.Soc. 2006, 128, 4594. (b) Chen, C.; Zhu, S.-F.; Liu, B.; Wang, L.-X.; Zhou, Q.-L. J.Am. Chem.Soc. 2007, 129, 12616. (c) Zhu, S.-F.; Chen, C.; Cai, Y.; Zhou, Q.-L. Angew.Chem., Int.Ed. 2008, 47, 932. (d) Zhu, S.-F.; Song, X.-G.; Li, Y.; Cai, Y.; Zhou, Q.-L. J. Am.Chem.Soc. 2010, 132, 16374. (e) Zhu, S.-F.; Cai, Y.; Mao, H.-X.; Xie, J.-H.; Zhou, Q.-L. Nat.Chem. 2010, 2, 546. (f) Osako, T.; Panichakul, D.; Uozumi, Y. Org.Lett. 2012, 14, 194. (g) Song, X.-G.; Zhu, S.-F.; Xie, X.-L.; Zhou, Q.-L. Angew.Chem., Int.Ed. 2013, 52, 2555. (h) Xie, X.-L.; Zhu, S.-F.; Guo, J.-X.; Cai, Y.; Zhou, Q.-L. Angew.Chem., Int.Ed. 2014, 53, 2978. (i) Tan, F.; Liu, X.-H.; Hao, X.-Y.; Tang, Y.; Lin, L.-L.; Feng, X.-M. ACS Catal. 2016, 6, 6930. (j) Zhang, Y.-L.; Yao, Y.; He, L.; Liu, Y.; Shi, L. Adv.Synth. Catal. 2017, 359, 2754. (k) Huang, D.-R.; Xu, G.-Y.; Peng, S.-Y.; Sun, J.-T. Chem.Commun. 2017, 53, 3197.
4. [4]
  For preparation and applications of α-diazoketones in catalytic asymmetric reactions, see: (a) Doyle, M. P.; McKervey, M. A.; Ye, T. Modern Catalytic Methods for Organic Synthesis with Diazo Compounds, Wiley, New York, 1998. (b) Doyle, M. P.; Eismont, M. Y.; Zhou, Q.-L. Russ. Chem.Bull. 1997, 46, 955. (c) Kitagaki, S.; Anada, M.; Kataoka, O.; Matsuno, K.; Umeda, C.; Watanabe, N.; Hashimoto, S. J.Am. Chem.Soc. 1999, 121, 1417. (d) Barberis, M.; Pérez-Prieto, J.; Stiriba, S.-E.; Lahuerta, P. Org.Lett. 2001, 3, 3317. (e) Hwang, C. H.; Chong, Y. H.; Song, S. Y.; Kwak, H. S.; Lee, E. Chem. Commun. 2004, 816. (f) Suga, H.; Ishimoto, D.; Higuchi, S.; Ohtsuka, M.; Arikawa, T.; Tsuchida, T.; Kakehi, A.; Baba, T. Org.Lett. 2007, 9, 4359. (g) Taber, D. F.; Tian, W. J.Org.Chem. 2008, 73, 7560. (h) Denton, J. R.; Davies, H. M. L. Org.Lett. 2009, 11, 787. (i) Xu, X.; Qian, Y.; Yang, L.; Hu, W. Chem.Commun. 2011, 47, 797. (j) Qian, Y.; Jing, C.; Liu, S.; Hu, W. Chem. Commun. 2013, 49, 2700. (k) Taber, D. F.; Paquette, C. M.; Gu, P.; Tian, W. J.Org.Chem. 2013, 78, 9772.
5. [5]
  For non-enantioselective O—H insertion using α-diazoketones as carbene precursors, see: (a) Yates, P. J.Am.Chem.Soc. 1952, 74, 5376. (b) Shinada, T.; Kawakami, T.; Sakai, H.; Takada, I.; Ohfune, Y. Tetrahedron Lett. 1998, 39, 3757. (c) Nelson, T. D.; Song, Z. J.; Thompson, A. S.; Zhao, M.; DeMarco, A.; Reamer, R. A.; Huntington, M. F.; Grabowsk, E. J.; Reider, P. J. Tetrahedron Lett. 2000, 41, 1877. (d) Muthusamy, S.; Babu, S. A.; Gunanathan, C. Tetrahedron Lett. 2002, 43, 3133. (e) Ronan, B.; Bacqué, E.; Barrière, J. C. Tetrahedron 2004, 60, 3819. (f) Muthusamy, S.; Gnanaprakasam, B.; Suresh, E. Org.Lett. 2005, 7, 4577. (g) Jung, J. C.; Avery, M. A. Tetrahedron Lett. 2006, 47, 7969.
6. [6]
7. [7]
8. [8]
  Franklin, A. D.; Haque, M. S.; Robert, M. P. J. Org.Chem. 1989, 54, 2021. doi: 10.1021/jo00269a054
9. [9]
  Yin, J.-J.; Mark, A. H.; Karen, M. C.; Joseph, D. A. J.Org.Chem. 2006, 71, 840. doi: 10.1021/jo052121t
10. [10]
  For details of DFT calculation, see supporting information and relevant literature ref. 6c.
11. [11]
  Liang, Y.; Zhou, H.-L.; Yu, Z.-X. J.Am.Chem.Soc. 2009, 131, 17783. doi: 10.1021/ja9086566
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]
  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
3. [3]
  Jiaqi AN , Yunle LIU , Jianxuan SHANG , Yan GUO , Ce LIU , Fanlong ZENG , Anyang LI , Wenyuan WANG . Reactivity of extremely bulky silylaminogermylene chloride and bonding analysis of a cubic tetragermylene. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1511-1518. doi: 10.11862/CJIC.20240072
4. [4]
  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
5. [5]
  Chi Li , Jichao Wan , Qiyu Long , Hui Lv , Ying Xiong . N-Heterocyclic Carbene (NHC)-Catalyzed Amidation of Aldehydes with Nitroso Compounds. University Chemistry, 2024, 39(5): 388-395. doi: 10.3866/PKU.DXHX202312016
6. [6]
  Jin Tong , Shuyan Yu . Crystal Engineering for Supramolecular Chirality. University Chemistry, 2024, 39(3): 86-93. doi: 10.3866/PKU.DXHX202308113
7. [7]
  Qiuting Zhang , Fan Wu , Jin Liu , Zian Lin . Chromatographic Stationary Phase and Chiral Separation Using Frame Materials. University Chemistry, 2025, 40(4): 291-298. doi: 10.12461/PKU.DXHX202405174
8. [8]
  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
9. [9]
  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
10. [10]
  Guojie Xu , Fang Yu , Yunxia Wang , Meng Sun . Introduction to Metal-Catalyzed β-Carbon Elimination Reaction of Cyclopropenones. University Chemistry, 2024, 39(8): 169-173. doi: 10.3866/PKU.DXHX202401060
11. [11]
  Haiying Wang , Andrew C.-H. Sue . How to Visually Identify Homochiral Crystals. University Chemistry, 2024, 39(3): 78-85. doi: 10.3866/PKU.DXHX202309004
12. [12]
  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
13. [13]
  Hong RAO , Yang HU , Yicong MA , Chunxin LÜ , Wei ZHONG , Lihua DU . Synthesis and in vitro anticancer activity of phenanthroline-functionalized nitrogen heterocyclic carbene homo- and heterobimetallic silver/gold complexes. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2429-2437. doi: 10.11862/CJIC.20240275
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]
  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
16. [16]
  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
17. [17]
  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
18. [18]
  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
19. [19]
  Yue Zhao , Yanfei Li , Tao Xiong . Copper Hydride-Catalyzed Nucleophilic Additions of Unsaturated Hydrocarbons to Aldehydes and Ketones. University Chemistry, 2024, 39(4): 280-285. doi: 10.3866/PKU.DXHX202309001
20. [20]
  Yunhao Zhang , Yinuo Wang , Siran Wang , Dazhen Xu . Progress in Selective Construction of Functional Aromatics from Nitrogenous Cycloalkanes. University Chemistry, 2024, 39(11): 136-145. doi: 10.3866/PKU.DXHX202401083

Get Citation

PDF

XML

Metrics

PDF Downloads(23)
Abstract views(983)
HTML views(237)

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