Advances in the Catalytic Asymmetric Synthesis of Chiral Spiroketals

doi:10.6023/cjoc202205001

Abstract

As an unique spiro skeleton, spiroketals are ubiquitous motifs in many natural products, biologically active molecules, and privileged chiral ligands. The development of efficient synthetic methods for the preparation of spiroketals has long been a hot research topic in organic synthesis. In particular, the remarkable advances regarding the catalytic asymmetric synthesis of chiral spiroketals have been achieved over the past decade. The progress in the field of catalytic asymmetric synthesis of chiral spiroketals is summarized according to the reaction types. The future development direction of this field is also prospected.

Key words: asymmetric catalysis, enantioselectivity, spiroketals

Cite this article

Hui Yan, Man Zhang, Lin Li, Teng Hu, Wulin Yang. Advances in the Catalytic Asymmetric Synthesis of Chiral Spiroketals[J]. Chinese Journal of Organic Chemistry, 2022, 42(11): 3640-3657.

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Fig. & Tab. 31

Scheme 1. Representative natural products and biologically active molecules containing chiral spiroketal skeletons

Scheme 2. Selected examples of chiral ligands containing chiral spiroketal skeletons

Scheme 3. Four different spatial conformations of [6,6]- spiroketal

Scheme 4. Asymmetric intramolecular spiroketalization catalyzed by novel phosphoramide and reaction mechanism

Scheme 5. Chiral phosphoric acid-catalyzed asymmetric intramolecular spiroketalization

Scheme 6. Synthesis of chiral spiroketals via chiral iridium complex catalyzed asymmetric hydrogenation/spiroketalization

Scheme 7. Synthesis of spiroketals via asymmetric hydrogenation of Bn-protected bis(2-hydroxyarylidenes) followed by deprotection-spiroketalization process

Scheme 8. Asymmetric construction of bisbenzannulated [6,6]-spiroketal skeletons from diarylideneacetones

Scheme 9. One-pot enantioselective synthesis of spiroketals

Scheme 10. Total synthesis of Bistramide A

Scheme 11. Gold/CPA catalyzed intramolecular reaction to synthesize chiral spiroketals

Scheme 12. Organocatalytic asymmetric intramolecular hemiacetalization/Michael addition cascade reaction to synthesize chiral spiroketals

Scheme 13. Organocatalytic asymmetric intramolecular nucleophilic substitution reaction to synthesize bisbenzannulated spiroketals

Scheme 14. Ir-catalyzed asymmetric intramolecular hemiacetalization/allylic substitution cascade reaction to synthesize chiral spiroketals

Scheme 15. Total synthesis of (＋)-Broussonetine H

Scheme 16. Organocatalytic intramolecular hemiacetalization/oxa-Michael addition cascade reaction to synthesize chiral spiroketals

Scheme 17. Intramolecular hemiacetalization/oxa-Michael addition cascade reaction to synthesize chiral [5,6]-aromatic spiroketals

Scheme 18. Asymmetric synthesis of spiroketals via oxidation/hemiacetalization/oxa-Michael addition of phenol derivatives

Scheme 19. Catalytic asymmetric halocyclization cascade reaction of olefinic keto-acids to synthesize chiral spiroketals and reaction mechanism

Scheme 20. Organocatalytic enantioselective synthesis of spiroketal lactones bearing axial and central chirality

Scheme 21. Lewis base catalyzed asymmetric intramolecular cyclization to synthesize chiral spiroketals

Scheme 22. Catalytic asymmetric synthesis of chiral spiroketals via hetero-Diels-Alder reaction

Scheme 23. Synthesis of chiral spiroketals through gold/CPA-catalyzed asymmetric cascade reaction and the reaction mechanism

Scheme 24. Asymmetric synthesis of chiral spiroketals through three-component cascade reaction between alkynols, anilines and glyoxylic acid and reaction mechanism

Scheme 25. Au/Ni relay catalysis enables asymmetric synthesis of spiroketals and spiroaminals and reaction mechanism

Scheme 26. Gold(I)/chiral Rh(III) Lewis acid relay catalysis enables asymmetric synthesis of spiroketals and spiroaminals

Scheme 27. Au/Ir catalyzed asymmetric cascade reaction to synthesize chiral spiroketals and spiroamines and the application

Scheme 28. Reaction mechanism of Au/Ir catalyzed asymmetric cascade reaction

Scheme 29. Au/Mg co-catalyzed asymmetric cascade reaction to synthesize chiral [6,6]-spiroketals and reaction mechanism

Scheme 30. Synthesis of chiral spiroketals through cyclopropionation/rearrangement cascade reaction

Scheme 31. Reaction mechanism of chiral spiro ketal compounds synthesized by cyclopropylation/rearrangement series reaction

References 47

[1]	(a) Zhu, S.-F.; Zhou, Q.-L. In Privileged Chiral Ligands and Catalysts, Ed.: Zhou, Q.-L., Wiley-VCH, Weinheim, 2011, pp. 137-170. pmid: 21975423
	(b) Ding, K.; Han, Z.; Wang, Z. Chem. Asian J. 2009, 4, 32. doi: 10.1002/asia.200800192 pmid: 21975423
	(c) Ramon, R. Chem. Soc. Rev. 2012, 41, 1060. doi: 10.1039/c1cs15156h pmid: 21975423
[2]	(a) Perron, F.; Albizati, K. F. Chem. Rev. 1989, 89, 1617. doi: 10.1021/cr00097a015
	(b) Wilsdorf, M.; Reissig, H. U. Angew. Chem., Int. Ed. 2012, 51, 9486. doi: 10.1002/anie.201203847
[3]	(a) Aho, J. E.; Pihko, P. M.; Rissa, T. K. Chem. Rev. 2005, 105, 4406. doi: 10.1021/cr050559n pmid: 31478048
	(b) Sperry, J.; Wilson, Z. E.; Rathwell, D. C. K.; Brimble, M. A. Nat. Prod. Rep. 2010, 27, 1117. doi: 10.1039/b911514p pmid: 31478048
	(c) Atkinson, D. J.; Brimble, M. A. Nat. Prod. Rep. 2015, 32, 811. doi: 10.1039/c4np00153b pmid: 31478048
	(d) Zhang, F.-M.; Zhang, S.-Y.; Tu, Y.-Q. Nat. Prod. Rep. 2018, 35, 75. doi: 10.1039/C7NP00043J pmid: 31478048
	(e) Gillard, R. M.; Brimble, M. A. Org. Biomol. Chem. 2019, 17, 8272. doi: 10.1039/c9ob01598a pmid: 31478048
[4]	Liu, W.-Z.; Ma, L.-Y.; Liu, D.-S.; Huang, Y.-L.; Wang, C.-H.; Shi, S.-S.; Pan, X.-H.; Song, X.-D.; Zhu, R.-X. Org. Lett. 2014, 16, 90. doi: 10.1021/ol403076s
[5]	Fujimoto, H.; Nozawa, M.; Okuyama, E.; Ishibashi, M. Chem. Pharm. Bull. 2002, 50, 330. doi: 10.1248/cpb.50.330
[6]	Li, J.; Li, L.; Si, Y.; Jiang, X.; Guo, L.; Che, Y. Org. Lett. 2011, 13, 2670. doi: 10.1021/ol200770k pmid: 21495643
[7]	Stierle, A. A.; Stierle, D. B.; Kelly, K. J. Org. Chem. 2006, 71, 5357; doi: 10.1021/jo060018d
[8]	Zhuravleva, O. I.; Sobolevskaya, M. P.; Afiyatullov, S. S.; Kirichuk, N. N.; Denisenko, V. A.; Dmitrenok, P. S.; Yurchenko, E. A.; Dyshlovoy, S. A. Mar. Drugs 2014, 12, 5930. doi: 10.3390/md12125930 pmid: 25501795
[9]	Namikoshi, M.; Kobayashi, H.; Yoshimoto, T.; Meguro, S. Chem. Lett. 2000, 29, 308. doi: 10.1246/cl.2000.308
[10]	(a) Twiner, M. J.; Doucette, G. J.; Pang, Y.; Fang, C.; Forsyth, C. J.; Miles, C. O. Mar. Drugs 2016, 14, 207. doi: 10.3390/md14110207
	(b) Fu, L.-L.; Zhao, X.-Y.; Ji, L.-D.; Xu, J. Toxicon 2019, 160, 1. doi: 10.1016/j.toxicon.2018.12.007
[11]	Reddy, C. R.; Srikanth, B.; Dilipkumar, U.; Rao, K. M. V.; Jagadeesh, B. Eur. J. Org. Chem. 2013, 525.
[12]	Trost, B. M.; Weiss, A. H. Angew. Chem., Int. Ed. 2007, 46, 7664. doi: 10.1002/anie.200702637
[13]	Uckun, F. M.; Mao, C.; Vassilev, A. O.; Huang, H.; Jan, S.-T. Bioorg. Med. Chem. Lett. 2000, 10, 541. pmid: 10741549
[14]	Scheepstra, M.; Andrei, S. A.; Unver, M. Y.; Hirsch, A. K. H.; Leysen, S.; Ottmann, C.; Brunsveld, L.; Milroy, L.-G. Angew. Chem., Int. Ed. 2017, 56, 5480. doi: 10.1002/anie.201612504
[15]	(a) Wang, X.; Ding, K. Chin. J. Chem. 2018, 36, 899. doi: 10.1002/cjoc.201800247
	(b) Wang, X.; Han, Z.; Wang, Z.; Ding, K. Acc. Chem. Res. 2021, 54, 668. doi: 10.1021/acs.accounts.0c00697
	(c) Li, J.; Chen, G.; Wang, Z.; Zhang, R.; Zhang, X.; Ding, K. Chem. Sci. 2011, 2, 1141. doi: 10.1039/c0sc00607f
[16]	(a) Argüelles, A. J.; Sun, S.; Budaitis, B. G.; Nagorny, P. Angew. Chem., Int. Ed. 2018, 57, 5325. doi: 10.1002/anie.201713304 pmid: 30207727
	(b) Huang, J.; Hong, M.; Wang, C.-C.; Kramer, S.; Lin, G.-Q.; Sun, X.-W. J. Org. Chem. 2018, 83, 12838. doi: 10.1021/acs.joc.8b01693 pmid: 30207727
[17]	(a) Rizzacasa, M. A.; Pollex, A. Org. Biomol. Chem. 2009, 7, 1053. doi: 10.1039/b819966n pmid: 19262920
	(b) Raju, B. R.; Saikia, A. K. Molecules 2008, 13, 1942. doi: 10.3390/molecules13081942 pmid: 19262920
	(c) Sperry, J.; Liu, Y.-C.; Brimble, M. A. Org. Biomol. Chem. 2010, 8, 29. pmid: 19262920
	(d) Palmes, J. A.; Aponick, A. Synthesis 2012, 44, 3699. doi: 10.1055/s-0032-1317489 pmid: 19262920
	(e) Quach, R.; Chorley, D. F.; Brimble, M. A. Org. Biomol. Chem. 2014, 12, 7423. doi: 10.1039/C4OB01325E pmid: 19262920
	(f) Quach, R.; Furkert, D. P.; Brimble, M. A. Org. Biomol. Chem. 2017, 15, 3098. doi: 10.1039/C7OB00496F pmid: 19262920
[18]	Čorić, I.; List, B. Nature 2012, 483, 315. doi: 10.1038/nature10932
[19]	(a) Sun, Z.; Winschel, G. A.; Borovika, A.; Nagorny, P. J. Am. Chem. Soc. 2012, 134, 8074. doi: 10.1021/ja302704m pmid: 26641317
	(b) Khomutnyk, Y. Y.; Argüelles, A. J.; Winschel, G. A.; Sun, Z.; Zimmerman, P. M.; Nagorny, P. J. Am. Chem. Soc. 2016, 138, 444. doi: 10.1021/jacs.5b12528 pmid: 26641317
[20]	Wang, X.; Han, Z.; Wang, Z.; Ding, K. Angew. Chem., Int. Ed. 2012, 51, 936; doi: 10.1002/anie.201106488
[21]	Wang, X.; Guo, P.; Wang, X.; Wang, Z.; Ding, K. Adv. Synth. Catal. 2013, 355, 2900. doi: 10.1002/adsc.201300380
[22]	Liu, N.; Zhu, W.; Yao, J.; Yin, L.; Lu, T.; Dou, X. ACS Catal. 2020, 10, 2596. doi: 10.1021/acscatal.9b05577
[23]	Han, X.; Floreancig, P. E. Angew. Chem., Int. Ed. 2014, 53, 11075. doi: 10.1002/anie.201406819
[24]	Rexit, A. A.; Mailikezati, M. Tetrahedron Lett. 2015, 56, 2651. doi: 10.1016/j.tetlet.2015.03.007
[25]	Yoneda, N.; Fukata, Y.; Asano, K.; Matsubara, S. Angew. Chem., Int. Ed. 2015, 54, 15497. doi: 10.1002/anie.201508405
[26]	Xue, J.; Zhang, H.; Tian, T.; Yin, K.; Liu, D.; Jiang, X.; Li, Y.; Jin, X.; Yao, X. Adv. Synth. Catal. 2016, 358, 370. doi: 10.1002/adsc.201500390
[27]	Hamilton, J. Y.; Rössler, S. L.; Carreira, E. M. J. Am. Chem. Soc. 2017, 139, 8082. doi: 10.1021/jacs.7b02856 pmid: 28598614
[28]	Rössler, S. L.; Schreib, B. S.; Ginterseder, M.; Hamilton, J. Y.; Carreira, E. M. Org. Lett. 2017, 19, 5533. doi: 10.1021/acs.orglett.7b02620 pmid: 28968123
[29]	Midya, A.; Maity, S.; Ghorai, P. Chem. Eur. J. 2017, 23, 11216. doi: 10.1002/chem.201701291
[30]	Roy, T. K.; Gorad, S. S.; Ghorai, P. Org. Lett. 2022, 24, 1889. doi: 10.1021/acs.orglett.2c00074
[31]	Reddy, R. R.; Panda, S.; Ghorai, P. J. Org. Chem. 2019, 84, 5357. doi: 10.1021/acs.joc.9b00371
[32]	Zheng, T.; Wang, X.; Ng, W.-H.; Tse, Y.-L. S.; Yeung, Y.-Y. Nat. Catal. 2020, 3, 993. doi: 10.1038/s41929-020-00530-9
[33]	Xu, S.; Huang, A.; Yang, Y.; Wang, Y.; Zhang, M.; Sun, Z.; Zhao, M.; Wei, Y.; Li, G.; Hong, L. Org. Lett. 2022, 24, 2978. doi: 10.1021/acs.orglett.2c00845
[34]	Hilby, K. M.; Denmark, S. E. J. Org. Chem. 2021, 86, 14250. doi: 10.1021/acs.joc.1c02271
[35]	Audrain, H.; Thorhauge, J.; Hazell, R. G.; Jørgensen, K.-A. J. Org. Chem. 2000, 65, 4487. pmid: 10959849
[36]	Yu, S.; Gao, L.; Yan, Y.; Yin, Z.; Shang, Y. Chin. J. Org. Chem. 2021, 41, 582. (in Chinese) doi: 10.6023/cjoc202006050
	( 余述燕, 高丽宏, 闫溢哲, 尹志刚, 商永嘉, 有机化学 2021, 41, 582.) doi: 10.6023/cjoc202006050
[37]	Wu, H.; He, Y.-P.; Gong, L.-Z. Org. Lett. 2013, 15, 460. doi: 10.1021/ol303188u
[38]	Cala, L.; Mendoza, A.; Fañanás, F. J.; Rodríguez, F. Chem. Commun. 2013, 49, 2715. doi: 10.1039/c3cc00118k
[39]	(a) Wang, X.; Dong, S.; Yao, Z.; Feng, L.; Daka, P.; Wang, H.; Xu, Z. Org. Lett. 2014, 16, 22. doi: 10.1021/ol4033286 pmid: 28474897
	(b) Liang, M.; Zhang, S.; Jia, J.; Tung, C.-H.; Wang, J.; Xu, Z. Org. Lett. 2017, 19, 2526. doi: 10.1021/acs.orglett.7b00804 pmid: 28474897
	(c) Teng, Q.; Qi, J.; Zhou, L.; Xu, Z.; Tung, C.-H. Org. Chem. Front. 2018, 5, 990. doi: 10.1039/C7QO01005B pmid: 28474897
	(d) Mao, W.; Lin, S.; Zhang, L.; Lu, H.; Jia, J.; Xu, Z. Org. Chem. Front. 2020, 7, 856. doi: 10.1039/D0QO00022A pmid: 28474897
[40]	Li, J.; Lin, L.; Hu, B.; Lian, X.; Wang, G.; Liu, X.; Feng, X. Angew. Chem., Int. Ed. 2016, 55, 6075. doi: 10.1002/anie.201601701
[41]	Gong, J.; Wan, Q.; Kang, Q. Adv. Synth. Catal. 2018, 360, 4031. doi: 10.1002/adsc.201800492
[42]	(a) Yang, W.-L.; Shang, X.-Y.; Luo, X.; Deng, W.-P. Angew. Chem., Int. Ed. 2022, 61, e202203661.
	(b) Yuen, D.-Y.; Yang, S.-H.; Brimble, M. A. Angew. Chem., nt. Ed. 2011, 50, 8350.
[43]	Yang, W.-L.; Wang, Y.-L.; Li, W.; Gu, B.-M.; Wang, S.-W.; Luo, X.; Tian, B.-X.; Deng, W.-P. ACS Catal. 2021, 11, 12557. doi: 10.1021/acscatal.1c03711
[44]	Chen, J.-R.; Hu, X.-Q.; Xiao, W.-J. Angew. Chem., Int. Ed. 2014, 53, 4038. doi: 10.1002/anie.201400018
[45]	(a) Wang, D.; Liu, S.; Lan, X.-C.; Paniagua, A.; Hao, W.-J.; Li, G.; Tu, S.-J.; Jiang, B. Adv. Synth. Catal. 2017, 359, 3186. doi: 10.1002/adsc.201700543
	(b) Liu, S.; Chen, K.; Lan, X.-C.; Hao, W.-J.; Li, G.; Tu, S.-J.; Jiang, B. Chem. Commun. 2017, 53, 10692. doi: 10.1039/C7CC05563C
	(c) Liu, S.; Lan, X.-C.; Chen, K.; Hao, W.-J.; Li, G.; Tu, S.-J.; Jiang, B. Org. Lett. 2017, 19, 3831. doi: 10.1021/acs.orglett.7b01705
	(d) Qiu, J.-K.; Hao, W.-J.; Li, G.; Jiang, B. Adv. Synth. Catal. 2018, 360, 1182. doi: 10.1002/adsc.201701149
	(e) Ji, C.-L.; Pan, Y.; Geng, F.-Z.; Hao, W.-J.; Tu, S.-J.; Jiang, B. Org. Chem. Front. 2019, 6, 474. doi: 10.1039/C8QO01277F
[46]	Ge, S.; Cao, W.; Kang, T.; Hu, B.; Zhang, H.; Su, Z.; Liu, X.; Feng, X. Angew. Chem., Int. Ed. 2019, 58, 4017. doi: 10.1002/anie.201812842
[47]	Dong, K.; Gurung, R.; Xu, X.; Doyle, M. P. Org. Lett. 2021, 23, 3955. doi: 10.1021/acs.orglett.1c01113

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