不对称催化合成手性1,2-双硼酸酯研究进展

doi:10.6023/cjoc202312014

摘要/Abstract

手性1,2-双硼酸酯是合成化学中重要的转化砌块, 其催化不对称合成引起了化学界的广泛关注. 近年来, 过渡金属和手性双醇催化的烯烃不对称双硼化反应已成为合成手性1,2-双硼酸酯的重要方法, 基于烯基双硼化合物的不对称氢化反应, 可以作为烯烃双硼化反应的补充来合成对应的目标产物. 同时, 烯烃或炔烃的硼化/官能团化也是构建这类化合物的另一种有效方法. 最近, 以偕二硼酸酯为起始物的催化不对称迁移增碳反应, 为手性1,2-双硼酸酯的合成提供了新的思路. 总结了手性1,2-双硼酸酯合成的最新研究进展及面临的挑战, 并对未来的研究方向进行了展望.

关键词: 手性1,2-双硼酸酯, 双硼化, 氢硼化, 硼化/官能团化, 偕二硼酸酯, 迁移偶联

Chiral 1,2-bis(boronic) esters are essential building blocks in the field of synthetic chemistry, and their catalytic asymmetric synthesis has attracted significant interest of chemists. Recently, asymmetric diboration of olefins, using transition metals and chiral diols, has emerged as the straightforward and atom-economical methods for producing highly valuable chiral 1,2-bis(boronic) esters. Asymmetric hydrogenation of vinyl bis(boronic) esters can be a complementary approach to asymmetric diboration for synthesizing these products. Additionally, borofunctionalization of alkenes or alkynes represents another effective strategy for constructing these highly valuable scaffolds. A recent innovation involves catalytic asymmetric migratory coupling reactions with gem-diborylalkanes, offering new avenues for synthesizing chiral 1,2-bis(boronic) esters. The latest developements and challenges in synthesizing these moleculeshis are summarized, and the potential future research directions in this field are prospected.

Key words: chiral 1,2-bis(boronic) esters, diborylation, hydroboration, borofunctionalization, gem-diborylalkanes, migratory coupling reactions

引用此文

吉崇磊, 高得伟. 不对称催化合成手性1,2-双硼酸酯研究进展[J]. 有机化学, 2024, 44(5): 1385-1402.

Chonglei Ji, Dewei Gao. Recent Advances in Catalytic Asymmetric Synthesis of Chiral 1,2-Bis(boronic) Esters[J]. Chinese Journal of Organic Chemistry, 2024, 44(5): 1385-1402.

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图/表 18

Figure 1. Synthetic potential of 1,2-bis(boronic) esters and the methods used to prepare these privileged scaffolds

Figure 2. Rhodium-catalyzed enantioselective diboration of alkenes

Figure 3. Enantioselective diboration of simple alkenes: reaction development and substrate scope

Figure 4. Rhodium-catalyzed enantioselective diboration of terminal alkenes

Figure 5. Pd-catalyzed enantioselective diboration of prochiral allenes

Figure 6. Palladium-catalyzed asymmetric diboration of allenes and subsequent transformations

Figure 7. Pt-catalyzed enantioselective diboration of terminal alkenes

Figure 8. Pt-catalyzed enantioselective diboration of 1,3-dienes

Figure 9. Pt-catalyzed enantioselective diboration of vinyl boronic esters

Figure 10. Pt-catalyzed stereoselective diboration of spirocyclobutenes

Figure 11. Carbohydrate-catalyzed enantioselective diboration of alkenes

Figure 12. Cu-catalyzed stereoselective diboration of alkenes and alkynes

Figure 13. Cu-catalyzed borofunctionalization of alkenes

Figure 14. Cu-catalyzed tandem borylation/1,2-addition

Figure 15. Cu-catalyzed enantioselective diboration of 1?chloro-1-trifluoromethylalkenes

Figure 16. Catalytic enantioselective hydrogenation of vinyl bis(boronates)

Figure 17. Our idea to construct chiral 1,2-bis(boronic) esters featuring acyclic, 1,3-stereocenters

Figure 18. Asymmetric synthesis of chiral 1,2-bis(boronic) esters featuring acyclic, 1,3-stereocenters

参考文献 42

[1]	(a) Caldwell, J. J. Clin. Pharmacol. 1992, 32, 925. pmid: 1447400
	(b) Jozwiak, K.; Lough, W. J.; Wainer, I. W. Drug Stereochemistry: Analytical Methods and Pharmacology, 3rd ed., Informa, New York, 2012. pmid: 1447400
	(c) Rentsch, K. M. J. Biochem. Biophys. Methods 2002, 54, 1. pmid: 1447400
[2]	(a) Hall, D. G. Boronic Acids: Preparation and Applications in Organic Synthesis, Medicine and Materials, 2nd ed., Wiley-VCH, Weinheim, Germany, 2011. pmid: 32612487
	(b) Trippier, P. C.; McGuigan, C. Med. Chem. Commun. 2010, 1, 183. pmid: 32612487
	(c) Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457. pmid: 32612487
	(d) Suzuki, A. Angew. Chem., Int. Ed. 2011, 50, 6722. doi: 10.1002/anie.201101379 pmid: 32612487
	(e) Xu, L.; Zhang, S.; Li, P. Chem. Soc. Rev. 2015, 44, 8848. pmid: 32612487
	(f) Brooks, W. L. A.; Sumerlin, B. S. Chem. Rev. 2016, 116, 1375. pmid: 32612487
	(g) Diner, C.; Szabó, K. J. J. Am. Chem. Soc. 2017, 139, 2. pmid: 32612487
	(h) Fyfe, J. W. B.; Watson, A. J. B. Chem 2017, 3, 31. pmid: 32612487
	(i) Rygus, J. P. G.; Crudden, C. M. J. Am. Chem. Soc. 2017, 139, 18124. pmid: 32612487
	(j) Namirembe, S.; Morken, J. P. Chem. Soc. Rev. 2019, 48, 3464. doi: 10.1039/c9cs00180h pmid: 32612487
	(k) He, Z.; Hu, Y.; Xia, C.; Liu, C. Org. Biomol. Chem. 2019, 17, 6099. pmid: 32612487
	(l) Kischkewitz, M.; Friese, F. W.; Studer, A. Adv. Synth. Catal. 2020, 362, 2077. doi: 10.1002/adsc.201901503 pmid: 32612487
	(m) Kalita, S. J.; Cheng, F.; Huang, Y.-Y. Adv. Synth. Catal. 2020, 362, 2778. pmid: 32612487
	(n) Yang, K.; Song, Q. Acc. Chem. Res. 2021, 54, 2298. pmid: 32612487
	(o) Yeung, K.; Mykura, R. C.; Aggarwal, V. K. Nat. Synth. 2022, 1, 117. pmid: 32612487
	(p) Jiang, X.-M.; Liu, X.-R.; Chen, A.; Zou, X.-Z.; Ge, J.-F.; Gao, D.-W. Eur. J. Org. Chem. 2022, e202101463. pmid: 32612487
[3]	(a) Viso, A.; Fernández de la Pradilla, R.; Tortosa, M. ACS Catal. 2022, 12, 10603.
	(b) Wang, X.; Wang, Y.; Huang, W.; Xia, C.; Wu, L. ACS Catal. 2021, 11, 1.
[4]	(a) Mlynarski, S. N.; Schuster, C. H.; Morken, J. P. Nature 2014, 505, 386. pmid: 33180502
	(b) Blaisdell, T. P.; Morken, J. P. J. Am. Chem. Soc. 2015, 137, 8712. doi: 10.1021/jacs.5b05477 pmid: 33180502
	(c) Crudden, C. M.; Ziebenhaus, C.; Rygus, J. P. G.; Ghozati, K.; Unsworth, P. J.; Nambo, M.; Voth, S.; Hutchinson, M.; Laberge, V. S.; Maekawa, Y.; Imao, D. Nat. Commun. 2016, 7, 11065. pmid: 33180502
	(d) Fawcett, A.; Nitsch, D.; Ali, M.; Bateman, J. M.; Myers, E. L.; Aggarwal, V. K. Angew. Chem., Int. Ed. 2016, 55, 14663. pmid: 33180502
	(e) Liu, X.; Sun, C.; Mlynarski, S.; Morken, J. P. Org. Lett. 2018, 20, 1898. pmid: 33180502
	(f) Davenport, E.; Fernandez, E. Chem. Commun. 2018, 54, 10104. pmid: 33180502
	(g) Fawcett, A.; Murtaza, A.; Gregson, C. H. U.; Aggarwal, V. K. J. Am. Chem. Soc. 2019, 141, 4573. pmid: 33180502
	(h) Namirembe, S.; Yan, L.; Morken, J. P. Org. Lett. 2020, 22, 9174. doi: 10.1021/acs.orglett.0c03134 pmid: 33180502
	(i) Willems, S.; Toupalas, G.; Reisenbauer, J. C.; Morandi, B. A. Chem. Commun. 2021, 57, 3909. pmid: 33180502
	(j) Mali, M.; Sharma, G. V. M.; Ghosh, S.; Roisnel, T.; Carboni, B.; Berrée, F. J. Org. Chem. 2022, 87, 7649. pmid: 33180502
	(k) Xu, N.; Kong, Z.; Wang, J. Z.; Lovinger, G. J.; Morken, J. P. J. Am. Chem. Soc. 2022, 144, 17815. pmid: 33180502
	(l) Zhang, M.; Lee, P. S.; Allais, C.; Singer, R. A.; Morken, J. P. J. Am. Chem. Soc. 2023, 145, 8308. pmid: 33180502
[5]	Ma, X.; Murray, B.; Biscoe, M. R. Nat. Rev. Chem. 2020, 4, 584.
[6]	Blair, D. J.; Tanini, D.; Bateman, J. M.; Scott, H. K.; Myers, E. L.; Aggarwal, V. K. Chem. Sci. 2017, 8, 2898.
[7]	(a) Coombs. J. R.; Morken. J. P. Angew. Chem., Int. Ed. 2016, 55, 2636. doi: 10.1002/anie.201507151 pmid: 30740530
	(b) Obligacion, J. V.; Chirik, P. J. Nat. Rev. Chem. 2018, 2, 15. doi: 10.1038/s41570-018-0001-2 pmid: 30740530
	(c) Wang, F.; Chen, P.; Liu, G. Acc. Chem. Res. 2018, 51, 2036. pmid: 30740530
	(d) Chen, J.-H.; Guo. J.; Lu, Z. Chin. J. Chem. 2018, 36, 1075. pmid: 30740530
	(e) Li, Z.-L.; Fang, G.-C.; Gu, Q.-S.; Liu, X.-Y. Chem. Soc. Rev. 2020, 49, 32. pmid: 30740530
[8]	Morgan, J. B.; Miller, S. P.; Morken, J. P. J. Am. Chem. Soc. 2003, 125, 8702.
[9]	Miller, S. P.; Morgan, J. B.; Nepveux, V. F. J.; Morken, J. P. Org. Lett. 2004, 6, 131.
[10]	Trudeau, S.; Morgan, J. B.; Shrestha, M.; Morken, J. P. J. Org. Chem. 2005, 70, 9538.
[11]	Toribatake, K.; Nishiyama, H. Angew. Chem., Int. Ed. 2013, 52, 11011. doi: 10.1002/anie.201305181 pmid: 24000239
[12]	Pelz, N. F.; Woodward, A. R.; Burks, H. E.; Sieber, J. D.; Morken, J. P. J. Am. Chem. Soc. 2004, 126, 16328.
[13]	Sieber, J. D.; Morken, J. P. J. Am. Chem. Soc. 2006, 128, 74.
[14]	Woodward, A. R.; Burks, H. E.; Chan, L. M.; Morken, J. P. Org. Lett. 2005, 7, 5505. pmid: 16288542
[15]	Pelz, N. F.; Morken, J. P. Org. Lett. 2006, 8, 4557.
[16]	Kliman, L. T.; Mlynarski, S. N.; Ferris, G. E.; Morken, J. P. J. Am. Chem. Soc. 2009, 131, 13210. doi: 10.1021/ja9047762 pmid: 19702329
[17]	(a) Kliman, L. T.; Mlynarski, S. N.; Morken, J. P. Angew. Chem., Int. Ed. 2012, 51, 512. pmid: 23862690
	(b) Coombs, J. R.; Haeffner, F.; Kliman, L. T.; Morken, J. P. J. Am. Chem. Soc. 2013, 135, 11222. doi: 10.1021/ja4041016 pmid: 23862690
[18]	Ferris, G. E.; Hong, K.; Roundtree, I. A.; Morken, J. P. J. Am. Chem. Soc. 2013, 135, 2501. doi: 10.1021/ja400506j pmid: 23390951
[19]	Coombs, J. R.; Zhang, L.; Morken, J. P. J. Am. Chem. Soc. 2014, 136, 16140. doi: 10.1021/ja510081r pmid: 25387002
[20]	(a) Byrom, N. T.; Grigg, R.; Kongkathip, B.; Reimer, G.; Wade, A. R. J. Chem. Soc., Perkin Trans. 1 1984, 1643.
	(b) Page, P. C. B.; Rayner, C. M.; Sutherland, I. O. Tetrahedron Lett. 1986, 27, 3535.
	(c) Page, P. C. B.; Rayner, C. M.; Sutherland, I. O. J. Chem. Soc., Chem. Commun. 1988, 356.
	(d) Page, P. C. B.; Rayner, C. M.; Sutherland, I. O. J. Chem. Soc., Perkin Trans. 1 1990, 1375.
	(e) Mayer, S. F.; Mang, H.; Steinreiber, A.; Saf, R.; Faber, K. Can. J. Chem. 2002, 80, 362.
[21]	Nóvoa, L.; Trulli, L.; Parra, A.; Tortosa, M. Angew. Chem., Int. Ed. 2021, 60, 11763. doi: 10.1002/anie.202101445 pmid: 33689223
[22]	(a) Bonet, A.; Sole, C.; Gulyás, H.; Fernández, E. Org. Biomol. Chem. 2012, 10, 6621.
	(b) Bonet, A.; Pubill-Ulldemolins, C.; Bo, C.; Gulyás, H.; Fernández, E. Angew. Chem., Int. Ed. 2011, 50, 7158.
[23]	Fang, L.; Yan, L.; Haeffner, F.; Morken, J. P. J. Am. Chem. Soc. 2016, 138, 2508.
[24]	Yan, L.; Meng, Y.; Haeffner, F.; Leon, R. M.; Crockett, M. P.; Morken, J. P. J. Am. Chem. Soc. 2018, 140, 3663. doi: 10.1021/jacs.7b12316 pmid: 29442502
[25]	Yan, L.; Morken, J. P. Org. Lett. 2019, 21, 3760. doi: 10.1021/acs.orglett.9b01204 pmid: 31066564
[26]	Lee, Y.; Jang, H.; Hoveyda, A. H. J. Am. Chem. Soc. 2009, 131, 18234.
[27]	Lee, Y.; Hoveyda, A. H. J. Am. Chem. Soc. 2009, 131, 3160.
[28]	Jung, H.-Y.; Yun, J. Org. Lett. 2012, 14, 2606.
[29]	Zanghi, J. M.; Liu, S.; Meek, S. J. Org. Lett. 2019, 21, 5172.
[30]	Radomkit, S.; Liu, Z.; Closs, A.; Mikus, M. S.; Hoveyda, A. H. Tetrahedron 2017, 73, 5011.
[31]	Lee, H.; Lee, S.; Yun, J. ACS Catal. 2020, 10, 2069.
[32]	Green, J. C.; Joannou, M. V.; Murray, S. A.; Zanghi, J. M.; Meek, S. J. ACS Catal. 2017, 7, 4441.
[33]	Fan, Z.; Ye, M.; Wang, Y.; Qiu, J.; Li, W.; Ma, X.; Yang, K.; Song, Q. ACS Cent. Sci. 2022, 8, 1134.
[34]	Morgan, J. B.; Morken, J. P. J. Am. Chem. Soc. 2004, 126, 15338.
[35]	Paptchikhine, A.; Cheruku, P.; Engman, M.; Andersson, P. G. Chem. Commun. 2009, 5996.
[36]	(a) Allen, A. E.; MacMillan, D. W. C. Chem. Sci. 2012, 3, 633.
	(b) Pye, D. R.; Mankad, N. P. Chem. Sci. 2017, 8, 1705.
	(c) Fu, J.; Huo, X.; Li, B.; Zhang, W. Org. Biomol. Chem. 2017, 15, 9747.
	(d) Kim, U. B.; Jung, D. J.; Jeon, H. J.; Rathwell, K.; Lee, S.-g. Chem. Rev. 2020, 120, 13382.
	(e) Tian, F.; Zhang, J.; Yang, W.-L.; Deng, W.-P. Chin. J. Org. Chem. 2020, 40, 3262.
	(f) Huo, X.; Li, G.; Wang, X.; Zhang, W. Angew. Chem., Int. Ed. 2022, 61, e202210086.
	(g) Wei, L.; Wang, C.-J. Chin. J. Chem. 2021, 39, 15.
	(h) Martínez, S.; Veth, L.; Lainer, B.; Dydio, P. ACS Catal. 2021, 11, 3891.
	(i) Wei, L.; Wang, C.-J. Chem. Catal. 2023, 3, 100455.
[37]	(a) Wang, Y.; Liu, X.; Deng, L. J. Am. Chem. Soc. 2006, 128, 3928. pmid: 26662073
	(b) Wang, B.; Wu, F.; Wang, Y.; Liu, X.; Deng, L. J. Am. Chem. Soc. 2007, 129, 768. pmid: 26662073
	(c) Zhu, B.; Lee, R.; Li, J.; Ye, X.; Hong, S.-N.; Qiu, S.; Coote, M. L.; Jiang, Z. Angew. Chem., Int. Ed. 2016, 55, 1299. doi: 10.1002/anie.201507796 pmid: 26662073
	(d) Li, Z.; Hu, B.; Wu, Y.; Fei, C.; Deng, L. Proc. Natl. Acad. Sci. U. S. A. 2018, 115, 1730. pmid: 26662073
	(e) Trost, B. M.; Zell, D.; Hohn, C.; Mata, G.; Maruniak, A. Angew. Chem., Int. Ed. 2018, 57, 12916. pmid: 26662073
	(f) Trost, B. M.; Schultz, J. E.; Chang, T.; Maduabum, M. R. J. Am. Chem. Soc. 2019, 141, 9521. pmid: 26662073
	(g) Yang, S.-Q.; Wang, Y.-F.; Zhao, W.-C.; Lin, G.-Q.; He, Z.-T. J. Am. Chem. Soc. 2021, 143, 7285. pmid: 26662073
	(h) Zhang, J.; Huo, X.; Xiao, J.; Zhao, L.; Ma, S.; Zhang, W. J. Am. Chem. Soc. 2021, 143, 12622. pmid: 26662073
	(i) Dai, J.; Li, L.; Ye, R.; Wang, S.; Wang, Y.; Peng, F.; Shao, Z. Angew. Chem., Int. Ed. 2023, 62, e202300756. pmid: 26662073
[38]	(a) Miralles, N.; Maza, R. J.; Fernández, E. Adv. Synth. Catal. 2018, 360, 1306. pmid: 33319887
	(b) Nallagonda, R.; Padala, K.; Masarwa, A. Org. Biomol. Chem. 2018, 16, 1050. doi: 10.1039/c7ob02978k pmid: 33319887
	(c) Wu, C.; Wang, J. Tetrahedron Lett. 2018, 59, 2128. pmid: 33319887
	(d) Cuenca, A. B.; Fernández, E. Chem. Soc. Rev. 2021, 50, 72. doi: 10.1039/d0cs00953a pmid: 33319887
	(e) Corro, M.; Salvado, O.; González, S.; Dominguez-Molano, P.; Fernández, E. Eur. J. Inorg. Chem. 2021, 2802. pmid: 33319887
	(f) Jo, W.; Lee, J. H.; Cho, S. H. Chem. Commun. 2021, 57, 4346. pmid: 33319887
	(g) Lee, Y.; Han, S.; Cho, S. H. Acc. Chem. Res. 2021, 54, 3917. pmid: 33319887
	(h) Zhang, C.; Hu, W.; Morken, J. P. ACS Catal. 2021, 11, 10660. pmid: 33319887
	(i) Paul, S.; Das, K. K.; Aich, D.; Manna, S.; Panda, S. Org. Chem. Front. 2022, 9, 838. pmid: 33319887
[39]	(a) Zhang, L.; Lovinǵer, G. J.; Edelstein, E. K.; Szymaniak, A. A.; Chierchia, M. P.; Morken, J. P. Science 2016, 351, 70. pmid: 31062812
	(b) Lovinger, G. J.; Aparece, M. D.; Morken, J. P. J. Am. Chem. Soc. 2017, 139, 3153. doi: 10.1021/jacs.6b12663 pmid: 31062812
	(c) Chierchia, M.; Law, C.; Morken, J. P. Angew. Chem., Int. Ed. 2017, 56, 11870. doi: 10.1002/anie.201706719 pmid: 31062812
	(d) Zhang, X.; Gao, C.; Morken, J. P. J. Am. Chem. Soc. 2023, 145, 16344. pmid: 31062812
	(e) For a review, see: Namirembe, S.; Morken, J. P. Chem. Soc. Rev. 2019, 48, 3464. doi: 10.1039/c9cs00180h pmid: 31062812
[40]	(a) Davis, C. R.; Luvaga, I. K.; Ready, J. M. J. Am. Chem. Soc. 2021, 143, 4921.
	(b) Davis, C. R.; Fu, Y.; Liu, P.; Ready, J. M. J. Am. Chem. Soc. 2022, 144, 16118.
[41]	(a) Ge, J.-F.; Zou, X.-Z.; Liu, X.-R.; Ji, C.-L.; Zhu, X.-Y.; Gao, D.-W. Angew. Chem., Int. Ed. 2023, 62, e202307447.
	(b) Chen, A.; Qiao, Y.; Gao, D.-W. Angew. Chem., Int. Ed. 2023, 62, e202312605.
[42]	Jiang, X.-M.; Ji, C.-L.; Ge, J.-F.; Zhao, J.-H.; Zhu, X.-Y.; Gao, D.-W. Angew. Chem., Int. Ed. 2024, 63, e202318441.