过渡金属不对称催化通过C-O键形成合成手性叔烷基醚的研究进展

doi:10.6023/cjoc202604011

摘要/Abstract

手性叔烷基醚作为一类重要的结构单元,广泛存在于天然产物、药物分子及具有生物活性的小分子中. 由于含有四取代的碳立体中心,该类结构的对映选择性的合成具有挑战性.近年来,随着新型手性催化剂的发展与反应设计的不断创新,该类结构的不对称合成取得了突破性进展. 本文从反应类型和过渡金属催化剂种类出发,系统综述了基于不对称亲核取代反应、烯烃烷氧基化反应、酮环加成/环化反应、C-H键官能化和卡宾O-H插入串联反应等通过C-O键的形成合成手性叔烷基醚的研究进展,重点阐述了各类反应的设计思路、催化体系、底物适用范围及机理,并对该领域目前面临的挑战及未来发展方向进行了展望.

关键词: 不对称催化, 过渡金属催化, 手性叔烷基醚, 四取代碳手性中心, 不对称C-O键构建

Chiral tertiary alkyl ethers are important structural motifs widely found in natural products, drug molecules, and biologically active small molecules. Owing to the presence of sterically congested tetrasubstituted carbon stereocenters, the enantioselective synthesis of chiral tertiary alkyl ethers poses a significant challenge. In recent years, driven with the development of novel chiral catalysts and continuous innovation in reaction design, remarkable advances have been made in the asymmetric construction of such structures via C-O formation. In this review, we summarize these progresses based on reaction types and the transition metal-catalysts employed, including asymmetric nucleophilic substitution, olefin alkoxylation, cycloaddition/annulation of ketones, C-H bond functionalization and cascade carbene O-H insertion reaction. The review focuses on the design principles, catalyst systems, substrate scope, and proposed mechanisms of the discussed reactions. Furthermore, current challenges and future directions in the field are discussed.

Key words: asymmetric catalysis, transition-metal catalysis, chiral tertiary alkyl ether, tetrasubstituted carbon stereocenter, asymmetric construction of C-O bond

引用此文

郑浩宇, 李传莹, 周友运. 过渡金属不对称催化通过C-O键形成合成手性叔烷基醚的研究进展[J]. 有机化学, doi: 10.6023/cjoc202604011.

Zheng Haoyu, Li Chuan-Ying, Zhou You-Yun. Progress on Transition Metal-Catalyzed Asymmetric Synthesis of Chiral Tertiary Alkyl Ethers via C-O Bond Formation[J]. Chinese Journal of Organic Chemistry, doi: 10.6023/cjoc202604011.

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参考文献

[1] Maskeri M. A; O'Connor, M. J.; Jaworski, A. A.; Bay, A. V.; Scheidt, K. A. Angew. Chem. Int. Ed. 2018, 57, 17225.
[2] Domínguez de María P; van Gemert R.W.; Straathof, A. J. J.; Hanefeld, U. Nat. Prod. Rep. 2010, 27, 370.
[3] Kennemur J. L.; Maji R.; Scharf M. J.; List B. Chem.Rev. 2021, 121, 14649.
[4] Attard J. W.; Noel J. R.; Guan Y.; Mattson A. E. Org. Lett. 2023, 25, 2450.
[5] Shennan B. D.A.; Berheci, D.; Crompton, J. L.; Davidson, T. A.; Field, J. L.; Williams, B. A.; Dixon, D. J. Chem. Soc. Rev. 2022, 51, 5878.
[6] Shi Y.-J.; Hughes D. L.; McNamara, J. M. Tetrahedron Lett. 2003, 44, 3609.
[7] Shintou T; Mukaiyama T. J. Am. Chem. Soc. 2004, 126, 7359
[8] Cox, N; Uehling, M. R.; Haelsig K. T.; Lalic G. Angew. Chem. Int. Ed. 2013, 52, 4878.
[9] Huang H; Guo X; Hu W. Angew. Chem. Int. Ed. 2007, 46, 1337.
[10] Trost B. M.; Zhang T.; Sieber J. D. Chem. Sci. 2010, 1, 427.
[11] Zhang J.; Wei Y.-F.; Luo R.-S. J. Org. Chem. Res. 2017, 5, 51(in Chinese).
(张剑,魏一飞,罗人仕,有机化学研究,J. Org. Chem. Res. 2017, 5, 51.
[12] Yao C.-Z.; Tu, X.-Q. Jiang H.-J.; Li Q.; Yu J.Tetrahedron Lett. 2023, 126, 154639.
[13] Jørgensen K.A. Angew. Chem. Int. Ed. 2000, 39, 3558.
[14] Pellissier H. Tetrahedron 2009, 65, 2839.
[15] Zhang J.;Xu M.-H. Sci Sin Chim, 2023, 53, 447 (in Chinese).
(张君友,徐明华,中国科学:化学2023, 53, 447)
[16] Zhang J.; Song Y.; Zhang Z.; Zhang W.Asian J. Org. Chem. 2025, 14, e202400584.
[17] Nicolaou K. C.; Snyder S. A.; Montagnon T.; Vassilikogiannakis G. Angew. Chem. Int. Ed. 2002, 41, 1668.
[18] Yan J.; Zhou Z.; He Q.; Chen G.; Wei H.; Xie W. Org. Chem. Front. 2022, 9, 499.
[19] Fuji, K. Chem.Rev. 1993, 93, 2037.
[20] Quasdorf K. W.; Overman L. E.Nature. 2014, 516, 181.
[21] Zhang Y.-P.; You, Y; Yin J.-Q.; Wang, Z.-H; Zhao J.-Q.; Li Q.; Yuan, W.-C. Eur. J. Org.Chem. 2023, 26, e202300728.
[22] Mizuguchi E.; Achiwa K. Chem. Pharm. Bull. 1997, 45, 1209.
[23] Trost B. M; McEachern, E. J.; Toste, F. D. J. Am. Chem. Soc. 1998, 120, 12702.
[24] Trost B. M; Toste F. D.J.Am.Chem.Soc. 1998, 120, 9074.
[25] Trost, B. M; Shen, H.C.; Dong, L; Surivet J.-P.J. Am. Chem. Soc. 2003, 125, 9276.
[26] Trost, B. M; Shen, H. C.; Dong, L; Surivet J.-P.; Sylvain C. J.Am.Chem.Soc. 2004, 126, 11966.
[27] Uria, U; Vila, C; Lin, M. Y.; Rueping M. Chem. Eur. J. 2014, 20, 13913.
[28] Tsai C. C.; Sandford C.; Wu T.; Chen B.; Sigman M. S.; Toste, F. D. Angew.Chem. Int.Ed. 2020, 59, 14647.
[29] Khan A.; Zheng R.; Kan Y.; Ye J.; Xing J.; Zhang Y. J. Angew. Chem. Int.Ed. 2014, 53, 6439.
[30] Xu H.; Khan S.; Li H.; Wu X.; Zhang Y. J. Org. Lett. 2019, 21, 214.
[31] Khan A.; Khan S.; Khan I.; Zhao C.; Mao Y.; Chen Y.; Zhang Y. J.J. Am. Chem. Soc. 2017, 139, 10733.
[32] Xie J.; Guo W.; Cai A.; Escudero-Adán, E. C.; Kleij, A. W. Org. Lett. 2017, 19, 6388.
[33] Khan S.;Li H.; Zhao C.; Wu X.; Zhang Y. J. Org. Lett. 2019, 21, 9457.
[34] Zhang J.-Y.; Chen J.-J.; Shen B.; Fang J.-H.; Du X.-Y.; Yang N.-Y.; Yang C.-J.; Liu W.-L.; Liu F.; Li Z.-L.; Gu Q.-S.; Dong Z.; Yu P.; Liu X.-Y.Nature Catalysis. 2025, 8, 919.
[35] Cheng Y.-F.; Dong X.-Y.; Gu Q.-S.; Yu, Z.-L; Liu, X.-Y. Angew. Chem. Int.Ed. 2017, 56, 8883.
[36] Cheng Y.-F.; Liu J.-R.; Gu Q.-S.; Yu Z.-L.; Wang J.; Li Z.-L.; Bian J.-Q.; Wen., H.-T.; Wang, X.-J.; Hong, X.; Liu, X.-Y. Nat. Catal. 2020, 3, 304.
[37] Hopkins B. A; Garlets Z. J; Wolfe J. P. Angew. Chem. Int.Ed. 2015, 54, 13390.
[38] Hu N.; Li, K; Wang Z.; Tang W. Angew. Chem. Int. Ed. 2016, 55, 5044.
[39] Zhu S.; Chen M.; Shen H.; Ding H.; Li W.; Zhang J. Chin. Chem. Lett. 2024, 35, 109879.
[40] Zhu S.; Ye, Z. ;Chen M.-J.; Wang L.; Wang Y.-Z.; Zhang K.-N.; Li W.-B.; Ding H.-M.; Li Z.; Zhang J. Nat.Commun. 2023, 14, 7611.
[41] Arai T.; Sugiyama N.; Masu H.; Kado S.; Yabe S.; Yamanaka M. Chem.Commun. 2014, 50, 8287.
[42] Arai T.; Horigane K.; Watanabe O.; Kakino J.; Sugiyama N.; Makino H.; Kamei Y.; Yabe S.; Yamanaka, M. iScience. 2019, 12, 280.
[43] Arai T.; Horigane K.; Suzuki, T. K; Itoh, R.; Yamanaka M. Angew. Chem. Int. Ed. 2020, 59, 12680.
[44] Suzuki T. K.; Yamanaka M.; Arai T. Org.Lett. 2022, 24, 3872.
[45] Uozumi Y.; Kato K.; Hayashi T. J.Am.Chem.Soc. 1997, 119, 5063.
[46] Zhang, Y.-J; Wang F.; Zhang W. J. Org. Chem. 2007, 72, 9208.
[47] Liu Q; Wen K; Zhang Z; Wu Z; Zhang YJ;Zhang W. Tetrahedron. 2012, 68, 5209.
[48] McDonald, R. I.; Liu, G.; Stahl, S. S. Chem. Rev. 2011, 111, 2981.
[49] Trend R. M.; Ramtohul Y. K.; Ferreira E. M.; Stoltz B. M. Angew. Chem. Int.Ed. 2003, 42, 2892.
[50] Trend R. M.; Ramtohul Y. K.; Stoltz B. M.J.Am.Chem.Soc. 2005, 127, 17778.
[51] Tietze L. F.; Sommer K. M.; Zinngrebe J.; Stecker F. Angew. Chem. Int. Ed. 2005, 44, 257.
[52] Chen D.; Berhane I. A.; Chemler S. R. Org. Lett. 2020, 22, 7409.
[53] Yao S.; Johannsen M.; Audrain H.; Hazell R. G.; Jørgensen K. A.J. Am. Chem. Soc. 1998, 120, 8599.
[54] Ghosh A. K.; Shirai M.Tetrahedron Lett. 2001, 42, 6231.
[55] Dalko P. I.; Moisan L.; Cossy J. Angew. Chem. Int. Ed. 2002, 41, 625.
[56] Furuno H.; Kambara T.; Tanaka Y.; Hanamoto T.; Kagawa T.; Inanaga J.Tetrahedron Lett. 2003, 44, 6129.
[57] Hanhan N. V.;Ball‐Jones, N. R.; Tran, N. T.; Franz, A. K. Angew. Chem. Int. Ed. 2012, 51, 989.
[58] Trost B. M.; Bringley D. A.;Silverman S. M.J. Am. Chem. Soc. 2011, 133, 7664.
[59] Trost B. M.; Bringley D. A. Angew. Chem. Int.Ed. 2013, 52, 4466.
[60] Trost B. M.; Mata, G. Angew. Chem. Int.Ed. 2018, 57, 12333.
[61] Trost B. M.; Wang Y.; Hung C.-I. Nat. Chem. 2020, 12, 294.
[62] Reissig H.-U.; Zimmer R. Chem.Rev. 2003, 103, 1151.
[63] Benfatti F.; de Nanteuil, F.; Waser, J. Chem. Eur. J. 2012, 18, 4844.
[64] Mei L.-y.; Wei, Y.; Xu, Q.; Shi, M. Organometallics. 2013, 32, 3544.
[65] Liu K.; Yang J.; Li X. Org.Lett. 2021, 23, 826.
[66] Ling Z.; Wang J.; Liu Y.-Z.; Deng W.-P. Org. Lett. 2026, 28, 2477
[67] Zhu T.-S.; Chen J.-P.; Xu, M.-H. Chem. Eur. J. 2013, 19, 865.
[68] Zhang Z.-F.; Zhu D.-X.; Chen W.-W.; Xu B.; Xu M.-H. Org. Lett. 2017, 19, 2726.
[69] Shibatomi K.; Kotozaki M.; Sasaki N.; Fujisawa I.; Iwasa S. Chem. Eur. J. 2015, 21, 14095.
[70] Wang P.-S.; Liu P.; Zhai Y.-J.; Lin H.-C.; Han Z.-Y.; Gong L.-Z.J. Am. Chem. Soc. 2015, 137, 12732.
[71] Hu W.; Xu X.; Zhou J.; Liu W.-J.; Huang H.; Hu J.; Yang L.; Gong L.-Z. J Am Chem Soc, 2008, 130, 7782.
[72] Xu X.; Zhou J.; Yang L.; Hu W. Chem Commun, 2008, 6564.
[73] Kang Z.; Zhang D.; Shou J.; Hu W. Org Lett, 2018, 20, 983.
[74] Xie X.; Bao M.; Chen K.; Xu X.; Hu W. Org. Chem. Front. 2022, 9, 2102.
[75] Che J.; Niu L.; Jia S.; Xing D.; Hu W. Nat.Commun. 2020, 11, 1511.
[76] Yu S.; Hua R.; Fu X.; Liu G.; Zhang D.; Jia S.; Qiu H.; Hu W. Org.Lett. 2019, 21, 5737.
[77] Yuan H.; Hong K. Liu,X.; Qian, Y.; Xu, X.; Hu, W. Chem. Commun. 2021, 57, 8043.
[78] Lv X.; Liu S.; Zhou S.; Dong G.; Xing D.; Xu X.; Hu, W. CCS Chem. 2021, 3, 1903.
[79] Hong K.; Shu J.; Dong S.; Zhang Z.; He Y.; Liu M.; Huang J.; Hu W.; Xu X. ACS Catal. 2022, 12, 14185.
[80] Zhang X.; Huang H.; Guo X.; Guan X.; Yang L.; Hu W. Angew.Chem Int Ed. 2008, 47: 6647-6649
[81] Gopi Krishna Reddy, A.; Niharika, P.; Zhou, S.; Jia, S.-K.; Shi, T.; Xu, X.; Qian, Y.; Hu, W. Org.Lett. 2020, 22, 2925.
[82] Liang X.-S.; Li R.-D.; Wang, X.-C. Angew. Chem. Int. Ed, 2019, 58, 13885.
[83] Hong K.; Dong S.; Xu X.; Zhang Z.; Shi T.; Yuan H.; Xu X.; Hu W. ACS Catal. 2021, 11, 6750.
[84] Zhou J.-J.; Liu L.-G.; Zhang Z.-T.; Dong H.-X.; Lu X.; Xu Z.; Zhu X.-Q.; Zhou B.; Ye, L.-W. Chin. Chem. Lett. 2025, 36, 110870.
[85] Meinwald J.; Labana S. S.; Chadha M. S.J. Am. Chem. Soc. 1963, 85, 582.