Advances of Chiral Spiro Skeleton-Based Bisnitrogen Ligands in Transition-Metal Catalysis

doi:10.6023/cjoc202210010

Abstract

Chiral spiro skeletons are recognized as a class of “privileged structures” of ligands. Studies toward these spiro ligands have significantly advanced the field of asymmetric catalysis. Bisnitrogen ligands bearing chiral spiro skeletons are reviewed and categorized according to the type of spirocyclic skeletons, including spiro[4.4]nonane-based bis(isoxazoline) ligands (SPRIX), spirobiindane-based bis(oxazoline) ligands (SpiroBox), spirobi(chroman)-based bis(amine) or bis(oxazoline) ligands (SPANamine or SPANBox), and spirocyclic pyrrolidine oxazoline ligands (SPDO). The synthesis and application of these four types of ligands and their applications in transition-metal catalysis are discussed in detail. Compared with the powerful and widely utilized chiral sprio phosphine ligands, the availability and application of spiro bisnitrogen ligands are relatively limited. Nevertheless, their features such as stability under acidic conditions and/or in the presence of an oxidant, superior capability of catalyzing carbene insertion into heteroatom-hydrogen bonds, provide insights and inspirations to the development of novel catalytic systems in asymmetric synthesis.

Key words: chiral spiro ligands, bisnitrogen ligands, asymmetric synthesis, transition-metal catalysis

Cite this article

Xudong Hu, Xinliang Zhang, Wenbo Liu. Advances of Chiral Spiro Skeleton-Based Bisnitrogen Ligands in Transition-Metal Catalysis[J]. Chinese Journal of Organic Chemistry, 2022, 42(10): 3102-3117.

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Fig. & Tab. 27

Figure 1. Representative structures of chiral spiro skeleton- based bisnitrogen ligands

Scheme 1. Synthesis of spiro bis(isoxazoline) ligands (SPRIX) and their applications in Pd-catalyzed Wacker-typed reactions

Scheme 2. Application of spiro bis(isoxazoline) ligands (SPRIX) in Pd-catalyzed tandem cyclization reaction

Scheme 3. Applications of Pd/SPRIX catalytic system in asymmetric amino-palladation and oxo-palladation reactions

Scheme 4. Pd/SPRIX-catalyzed asymmetric oxidative cyclization of enynes

Scheme 5. Pd/SPRIX-catalyzed asymmetric C—H activation/alkylation of indoles

Scheme 6. Spiro[4.4]nonane-based bis(oxazoline) and bis(pyrazole) ligands

Scheme 7. Synthesis of spirobiindane-based bis(oxazoline) ligands and their applications in insertion of carbenoids into N—H bonds

Scheme 8. Cu/SpiroBox-catalyzed enantioselective insertion of carbenoids into N—H bonds

Scheme 9. Cu/SpiroBox-catalyzed enantioselective insertion of carbenoids into O—H bonds of water

Scheme 10. Cu/SpiroBox-catalyzed enantioselective insertion of carbenoids into O—H bonds of alcohols

Scheme 11. Cu/SpiroBox-catalyzed enantioselective insertion of carbenoids into S—H bonds

Scheme 12. Fe/SpiroBox-catalyzed enantioselective insertion of carbenoids into O—H bonds

Scheme 13. Fe/SpiroBox-catalyzed enantioselective insertion of carbenoids into O—H bonds of phenols

Scheme 14. Cu/SIDIM-catalyzed enantioselective insertion of carbenoids into Si—H bonds

Scheme 15. Fe/HMSI-Box-catalyzed enantioselective insertion of carbenoids into Si—H bonds

Scheme 16. Cu/SpiroBox-catalyzed enantioselective cyclopropanation of allyl α-diazo-arylacetates

Scheme 17. Cu or Fe-catalyzed enantioselective intramolecular cyclopropanation of α-diazo-arylacetates and indoles

Scheme 18. Pd/SpiroBox-catalyzed enantioselective tandem cyclization reactions

Scheme 19. SPAN-based bis(amine) and bis(imine) ligands and their applications in asymmetric catalysis

Scheme 20. Synthesis of SPANBox ligands and their applications in Cu-catalyzed asymmetric α-hydroxylation reactions

Scheme 21. Applications of SPANBox ligands in Zn- and Cu-catalyzed asymmetric α-hydroxylation and α-chlorination reactions

Scheme 22. Synthesis of spirocyclic pyrrolidine oxazoline (SPDO) ligands

Scheme 23. Cu/SPDO-catalyzed enantioselective oxidative cross-coupling reaction of β-naphthols

Scheme 24. Plausible mechanism of Cu/SPDO-catalyzed cross-coupling reaction of β-naphthols

Scheme 25. Cu/SPDO-catalyzed enantioselective oxidative cross-coupling between β-naphthols and β-naphthylamines for the synthesis of BOBNINs

Scheme 26. Cu(II)/SPDO as a lewis acid catalyst in enantioselective addition reactions of quinone esters

References 56

[1]	(a) Torborg, C.; Beller, M. Adv. Synth. Catal. 2009, 351, 3027. doi: 10.1002/adsc.200900587
	(b) Lin, G.-Q.; Li, Y.-M.; Chan, A. S. C. Priciples and Applications of Asymmetric Synthesis, Wiley, New York, 2001.
[2]	(a) Liu, Y.; Li, W.; Zhang, J. Natl. Sci. Rev. 2017, 4, 326. doi: 10.1093/nsr/nwx064
	(b) Wang, X.; Han, Z.; Wang, Z.; Ding, K. Acc. Chem. Res. 2021, 54, 668. doi: 10.1021/acs.accounts.0c00697
	(c) Ojima, I. Catalytic Asymmetric Synthesis, Wiley-VCH, New York, 2000.
[3]	Ding, K.; Han, Z.; Wang, Z. Chem. Asian J. 2009, 4, 32. doi: 10.1002/asia.200800192
[4]	Xie, J.-H.; Zhou, Q.-L. Acta Chim. Sinica 2014, 72, 778. (in Chinese). doi: 10.6023/A14050364
	(谢建华, 周其林, 化学学报, 2014, 72, 778.) doi: 10.6023/A14050364
[5]	(a) Shibatomi, K.; Muto, T.; Sumikawa, Y.; Narayama, A.; Iwasa, S. Synlett 2009, 2009, 241. doi: 10.1055/s-0028-1087675 pmid: 22651700
	(b) Shibatomi, K.; Narayama, A.; Soga, Y.; Muto, T.; Iwasa, S. Org. Lett. 2011, 13, 2944. doi: 10.1021/ol201007e pmid: 22651700
	(c) Shibatomi, K.; Soga, Y.; Narayama, A.; Fujisawa, I.; Iwasa, S. J. Am. Chem. Soc. 2012, 134, 9836. doi: 10.1021/ja304806j pmid: 22651700
	(d) Narayama, A.; Shibatomi, K.; Soga, Y.; Muto, T.; Iwasa, S. Synlett 2013, 24, 375. doi: 10.1055/s-0032-1318027 pmid: 22651700
[6]	Srivastava, N.; Mital, A.; Kumar, A. J. Chem. Soc., Chem. Commun. 1992, 493.
[7]	(a) Chan, A. S. C.; Hu, W.; Pai, C.-C.; Lau, C.-P.; Jiang, Y.; Mi, A.; Yan, M.; Sun, J.; Lou, R.; Deng, J. J. Am. Chem. Soc. 1997, 119, 9570. doi: 10.1021/ja970955q
	(b) Jiang, Y.; Xue, S.; Li, Z.; Deng, J.; Mi, A.; Chan, A. S. C. Tetrahedron: Asymmetry 1998, 9, 3185.
	(c) Jiang, Y.; Xue, S.; Yu, K.; Li, Z.; Deng, J.; Mi, A.; Chan, A. S. C. J. Organomet. Chem. 1999, 586, 159. doi: 10.1016/S0022-328X(99)00257-0
[8]	Arai, M. A.; Arai, T.; Sasai, H. Org. Lett. 1999, 1, 1795. doi: 10.1021/ol9902881
[9]	Takizawa, S.; Yogo, J.; Tsujihara, T.; Onitsuka, K.; Sasai, H. J. Organomet. Chem. 2007, 692, 495. doi: 10.1016/j.jorganchem.2006.03.048
[10]	Arai, M. A.; Kuraishi, M.; Arai, T.; Sasai, H. J. Am. Chem. Soc. 2001, 123, 2907. pmid: 11456988
[11]	Shinohara, T.; Arai, M. A.; Wakita, K.; Arai, T.; Sasai, H. Tetrahedron Lett. 2003, 44, 711.
[12]	Muthiah, C.; Arai, M. A.; Shinohara, T.; Arai, T.; Takizawa, S.; Sasai, H. Tetrahedron Lett. 2003, 44, 5201. doi: 10.1016/S0040-4039(03)01250-4
[13]	Tsujihara, T.; Takenaka, K.; Onitsuka, K.; Hatanaka, M.; Sasai, H. J. Am. Chem. Soc. 2009, 131, 3452. doi: 10.1021/ja809965e pmid: 19275254
[14]	Abozeid, M. A.; Sairenji, S.; Takizawa, S.; Fujita, M.; Sasai, H. Chem. Commun. 2017, 53, 6887. doi: 10.1039/C7CC03199H
[15]	Takizawa, S.; Honda, Y.; Arai, M. A.; Kato, T.; Sasai, H. Heterocycles 2003, 60, 2551. doi: 10.3987/COM-03-9874
[16]	Kato, T.; Marubayashi, K.; Takizawa, S.; Sasai, H. Tetrahedron: Asymmetry 2004, 15, 3693.
[17]	Hu, A.-G.; Fu, Y.; Xie, J.-H.; Zhou, H.; Wang, L.-X.; Zhou, Q.-L. Angew. Chem., Int. Ed. 2002, 41, 2348.
	(b) Fu, Y.; Xie, J.-H.; Hu, A.-G.; Zhou, H.; Wang, L.-X.; Zhou, Q.-L. Chem. Commun. 2002, 480.
[18]	Liu, B.; Zhu, S.-F.; Wang, L.-X.; Zhou, Q.-L. Tetrahedron: Asymmetry 2006, 17, 634.
[19]	Birman, V. B.; Rheingold, A. L.; Lam, K.-C. Tetrahedron: Asymmetry 1999, 1, 1975.
[20]	Liu, B.; Zhu, S.-F.; Zhang, W.; Chen, C.; Zhou, Q.-L. J. Am. Chem. Soc. 2007, 129, 5834. doi: 10.1021/ja0711765
[21]	Zhu, S.-F.; Xu, B.; Wang, G.-P.; Zhou, Q.-L. J. Am. Chem. Soc. 2012, 134, 436. doi: 10.1021/ja2084493
[22]	Song, X.-G.; Ren, Y.-Y.; Zhu, S.-F.; Zhou, Q.-L. Adv. Synth. Catal. 2016, 358, 2366. doi: 10.1002/adsc.201600390
[23]	Zhu, S.-F.; Chen, C.; Cai, Y.; Zhou, O.-L. Angew. Chem., Int. Ed. 2008, 47, 932. doi: 10.1002/anie.200704651
[24]	Zhu, S.-F.; Song, X.-G.; Li, Y.; Cai, Y.; Zhou, Q.-L. J. Am. Chem. Soc. 2010, 132, 16374. doi: 10.1021/ja1078464
[25]	Zhu, S.-F.; Chen, W.-Q.; Zhang, Q.-Q.; Mao, H.-X.; Zhou, Q.-L. Synlett 2011, 2011, 919. doi: 10.1055/s-0030-1259710
[26]	Zhang, Y.-Z.; Zhu, S.-F.; Cai, Y.; Mao, H.-X.; Zhou, Q.-L. Chem. Commun. 2009, 5362.
[27]	(a) Brunner, H.; Wutz, K.; Doyle, M. P. Monatsh. Chem. 1990, 121, 755. doi: 10.1007/BF00808368
	(b) Galardon, E.; Roue, S.; Le Maux, P.; Simonneaux, G. Tetrahedron Lett. 1998, 39, 2333. doi: 10.1016/S0040-4039(98)00194-4
	(c) Zhang, X.-M.; Ma, M.; Wang, J.-B. ARKIVOC 2003, 2, 84.
[28]	Zhu, S.-F.; Cai, Y.; Mao, H.-X.; Xie, J.-H.; Zhou, Q.-L. Nat. Chem. 2010, 2, 546. doi: 10.1038/nchem.651
[29]	Maier, T. C.; Fu, G. C. J. Am. Chem. Soc. 2006, 128, 4594. doi: 10.1021/ja0607739
[30]	Xie, X.-L.; Zhu, S.-F.; Guo, J.-X.; Cai, Y.; Zhou, Q.-L. Angew. Chem., Int. Ed. 2014, 53, 2978. doi: 10.1002/anie.201309820
[31]	Zhang, Y.-Z.; Zhu, S.-F.; Wang, L.-X.; Zhou, Q.-L. Angew. Chem., Int. Ed. 2008, 47, 8496. doi: 10.1002/anie.200803192
[32]	Huang, H.; Yang, W.; Chen, Z.; Lai, Z.; Sun, J. Chem. Sci. 2019, 10, 9586. doi: 10.1039/c9sc03843d pmid: 32055332
[33]	Gu, H.; Han, Z.; Xie, H.; Lin, X. Org. Lett. 2018, 20, 6544. doi: 10.1021/acs.orglett.8b02868
[34]	Shen, J.-J.; Zhu, S.-F.; Cai, Y.; Xu, H.; Xie, X.-L.; Zhou, Q.-L. Angew. Chem., Int. Ed. 2014, 53, 13188. doi: 10.1002/anie.201406853
[35]	Gu, H.; Huang, S.; Lin, X. Org. Biomol. Chem. 2019, 17, 1154. doi: 10.1039/C8OB03065K
[36]	Xu, H.; Li, Y. P.; Cai, Y.; Wang, G. P.; Zhu, S. F.; Zhou, Q. L. J. Am. Chem. Soc. 2017, 139, 7697. doi: 10.1021/jacs.7b03086
[37]	Shu, W.; Ma, S. Chem. Commun. 2009, 6198.
[38]	Shu, W.; Yu, Q.; Ma, S. Adv. Synth. Catal. 2009, 351, 2807. doi: 10.1002/adsc.200900607
[39]	Bessel, C. A.; Aggarwal, P.; Marschilok, A. C.; Takeuchi, K. J. Chem. Rev. 2001, 101, 1031. pmid: 11709857
[40]	Freixa, Z.; Beentjes, M. S.; Batema, G. D.; Dieleman, C. B.; van Strijdonck, G. P. F.; Reek, J. Goubitz, K.; van Leeuwen, P. W. N. M. Angew. Chem., Int. Ed. 2003, 42, 1284. doi: 10.1002/anie.200390330
[41]	Sala, X.; Suarez, E. J. G.; Freixa, Z.; Benet-Buchholz, J.; van Leeuwen, P. W. N. M. Eur. J. Org. Chem. 2008, 6197.
[42]	Jacquet, O.; Clement, N. D.; Freixa, Z.; Ruiz, A.; Claver, C.; van Leeuwen, P. W. N. M. Tetrahedron: Asymmetry 2011, 22, 1490.
[43]	Li, J.; Chen, G.; Wang, Z.; Zhang, R.; Zhang, X.; Ding, K. Chem. Sci. 2011, 2, 1141. doi: 10.1039/c0sc00607f
[44]	Li, J.; Pan, W.; Wang, Z.; Zhang, X.; Ding, K. Adv. Synth. Catal. 2012, 354, 1980. doi: 10.1002/adsc.201200088
[45]	Han, Z.; Wang, Z.; Zhang, X.; Ding, K. Chin. Sci. Bull., 2010, 55, 2840. doi: 10.1007/s11434-010-4009-3
[46]	Caruso, A. J.; Lee, J. L. J. Org. Chem. 1997, 62, 1058. doi: 10.1021/jo961766d
[47]	Wang, X.; Han, Z.; Wang, Z.; Ding, K. Angew. Chem., Int. Ed. 2012, 51, 936. doi: 10.1002/anie.201106488
[48]	(a) Tian, J.-M.; Yuan, Y.-H.; Tu, Y.-Q.; Zhang, F.-M.; Zhang, X.-B.; Zhang, S.-H.; Wang, S.-H.; Zhang, X.-M. Chem. Commun. 2015, 51, 9979. doi: 10.1039/C5CC02765A
	(b) Chen, S.-K.; Ma, W.-Q.; Yan, Z.-B.; Zhang, F.-M.; Wang, S.-H.; Tu, Y.-Q.; Zhang, X.-M.; Tian, J.-M. J. Am. Chem. Soc. 2018, 140, 10099. doi: 10.1021/jacs.8b05386
[49]	Tian, J.-M.; Wang, A.-F.; Yang, J.-S.; Zhao, X.-J.; Tu, Y.-Q.; Zhang, S.-Y.; Chen, Z.-M. Angew. Chem., Int. Ed. 2019, 58, 11023. doi: 10.1002/anie.201903435
[50]	Li, X.; Hewgley, J. B.; Mulrooney, C. A.; Yang, J.; Kozlowski, M. C. J. Org. Chem. 2003, 68, 5500. doi: 10.1021/jo0340206
[51]	Zhao, X.-J.; Li, Z.-H.; Ding, T.-M.; Tian, J.-M.; Tu, Y.-Q.; Wang, A.-F.; Xie, Y.-Y. Angew. Chem., Int. Ed. 2021, 60, 7061. doi: 10.1002/anie.202015001
[52]	Xi, C.-C.; Zhao, X.-J.; Tian, J.- M.; Chen, Z.-M.; Zhang, K.; Zhang, F.-M.; Tu, Y.-Q.; Dong, J.-W. Org. Lett. 2020, 22, 4995. doi: 10.1021/acs.orglett.0c01558
[53]	Jing, Z.-R.; Liang, D.-D.; Tian, J.-M.; Zhang, F.-M.; Tu, Y.-Q. Org. Lett. 2021, 23, 1258. doi: 10.1021/acs.orglett.0c04241
[54]	Zhang, C.-S.; Shao, Y.-P.; Zhang, F.-M.; Han, X.; Zhang, X.-M.; Zhang, K.; Tu, Y.-Q. Chem. Sci., 2022, 13, 8429. doi: 10.1039/D2SC02079C
[55]	(a) Wang, X.; Guo, P.; Wang, X.; Wang, Z.; Ding, K. Adv. Synth. Catal. 2013, 355, 2900. doi: 10.1002/adsc.201300380
	(b) Li, S.; Zhang, J.-W.; Li, X.-L.; Cheng, D.-J.; Tan, B. J. Am. Chem. Soc. 2016, 138, 16561. doi: 10.1021/jacs.6b11435
	(c) Yin, L.; Xing, J.; Wang, Y.; Shen, Y.; Lu, T.; Hayashi, T.; Dou, X. Angew. Chem., Int. Ed. 2019, 58, 2474. doi: 10.1002/anie.201812266
[56]	(a) Varela, J. A.; Castedo, L.; Saá, C. Org. Lett. 1999, 1, 2141. doi: 10.1021/ol991195m
	(b) Wada, A.; Noguchi, K.; Hirano, M.; Tanaka, K. Org. Lett. 2007, 9, 1295. doi: 10.1021/ol070129e

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