Application of Planar Chiral Cyclopentadienyl Rhodium Catalysts without Chiral Substituents in Asymmetric C—H Activation

doi:10.6023/cjoc202410002

Abstract

Owing to the high stability, adjustability, and unique reactivity of chiral cyclopentadienyl rhodium (CpRh) catalysts, they are widely used in asymmetric C—H activation reactions for rapid construction of diverse and complex molecules bearing central chirality, planar chirality, axial chirality and helical chirality. According to whether the Cp ligand in chiral CpRh catalysts is chiral, the catalysts can be divided into chiral Cp-derived catalysts and prochiral Cp-derived catalysts. Currently, the development of the former has achieved great success, while research on the latter is relatively limited. The syntheses of planar chiral cyclopentadienyl rhodium catalysts without chiral substituents and their application in asymmetric C—H activation are summarized. The stereocontrol model and the mechanism are also discussed. Finally, the opportunities and challenges in developing the planar chiral cyclopentadienyl rhodium catalysts without chiral substituents are discussed.

Key words: cyclopentadienyl, rhodium, planar chirality, asymmetric catalysis, C—H activation

Cite this article

Yu Zou, Weicong Guo, Jun Wang. Application of Planar Chiral Cyclopentadienyl Rhodium Catalysts without Chiral Substituents in Asymmetric C—H Activation[J]. Chinese Journal of Organic Chemistry, 2025, 45(2): 466-476.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 11

Figure 1. Two types of Cp ligands for chiral CpRh catalysts

Scheme 1. Synthesis of planar chiral CpRh catalyst 5 and 8

Scheme 2. Application of (Rp)-5 in asymmetric [4＋2] annulation and stereocontrol model for the reaction

Scheme 3. Synthesis of planar chiral CpRh catalyst (Rp)-13 and (Sp)-13 and their application in asymmetric [4＋2] annulation

Scheme 4. Synthesis of planar chiral CpRh catalyst 23

Scheme 5. Synthesis of C—N axially chiral N-aryloxindoles using (Sp)-23a and stereocontrol model for the reaction

Scheme 6. Application of (Sp)-23e in asymmetric [4＋2] annulation and stereocontrol model for the reaction

Scheme 7. Design and synthesis of prochiral Cp ligands and chiral resolution of planar chiral CpRh complexes by chiral diene

Scheme 8. Synthesis of chiral hydrophenanthridinone catalyzed by 36b and stereocontrol model for the reaction

Scheme 9. Synthesis of chiral dihydroisoquinolinones catalyzed by 36d

Scheme 10. Synthesis of planar chiral indenyl rhodium catalyst 45, its application in enantioselective allylic C—H amidation and stereocontrol model for the reaction

References 24

[1]	(a) Liu, C.-X.; Yin, S.-Y.; Zhao, F.; Yang, H.; Feng, Z.; Gu, Q.; You, S.-L. Chem. Rev. 2023, 123, 10079. pmid: 32897713
	(b) Liang, H.; Wang, J. Chem.-Eur. J. 2023, 29, e202202461. pmid: 32897713
	(c) Zheng, Y.; Zheng, C.; Gu, Q.; You, S.-L. Chem Catal. 2022, 2, 2965. pmid: 32897713
	(d) Zhang, Q.; Wu, L.-S.; Shi, B.-F. Chem 2022, 8, 384. pmid: 32897713
	(e) Liu, B.; Romine, A. M.; Rubel, C. Z.; Engle, K. M.; Shi, B.-F. Chem. Rev. 2021, 121, 14957. pmid: 32897713
	(f) Woźniak, Ł.; Tan, J.-F.; Nguyen, Q.-H.; Madron du Vigné, A.; Smal, V.; Cao, Y.-X.; Cramer, N. Chem. Rev. 2020, 120, 10516. doi: 10.1021/acs.chemrev.0c00559 pmid: 32897713
	(g) Woźniak, Ł.; Cramer, N. Trends Chem. 2019, 1, 471. pmid: 32897713
	(h) Loup, J.; Dhawa, U.; Pesciaioli, F.; Wencel-Delord, J.; Ackermann, L. Angew. Chem., Int. Ed. 2019, 58, 12803. pmid: 32897713
	(i) Liao, G.; Zhou, T.; Yao, Q.-J.; Shi, B.-F. Chem. Commun. 2019, 55, 8514. pmid: 32897713
	(j) Saint-Denis, T. G.; Zhu, R.-Y.; Chen, G.; Wu, Q.-F.; Yu, J.-Q. Science 2018, 359, eaao4798. pmid: 32897713
	(k) Newton, C. G.; Wang, S.-G.; Oliveira, C. C.; Cramer, N. Chem. Rev. 2017, 117, 8908. pmid: 32897713
[2]	Hyster, T. K.; Knörr, L.; Ward, T. R.; Rovis, T. Science 2012, 338, 500. doi: 10.1126/science.1226132 pmid: 23112327
[3]	Ye, B.; Cramer, N. Science 2012, 338, 504.
[4]	(a) Yan, X.; Wang, J. Synthesis 2023, 55, 1309.
	(b) Satheeshkumar, A. K.; Usman, R.; Hapke, M. In Topics in Organometallic Chemistry, Springer Berlin Heidelberg, Berlin, Heidelberg, 2023, p. 1.
	(c) Pan, Y.; Qin, X.; Yuan, C.; Lu, Y. Chin. J. Org. Chem. 2023, 43, 924 (in Chinese).
	(潘彦年, 秦萧, 袁成凯, 鲁艺, 有机化学, 2023, 43, 924.) doi: 10.6023/cjoc202211039
	(d) Achar, T. K.; Al-Thabaiti, S. A.; Mokhtar, M.; Maiti, D. Chem Cat. 2023, 3, 100575.
	(e) Wang, Q.; Liu, C.-X.; Gu, Q.; You, S.-L. Sci. Bull. 2021, 66, 210.
	(f) Mas-Roselló, J.; Herraiz, A. G.; Audic, B.; Laverny, A.; Cramer, N. Angew. Chem., Int. Ed. 2021, 60, 13198.
	(g) Yoshino, T.; Satake, S.; Matsunaga, S. Chem.-Eur. J. 2020, 26, 7346.
	(h) Shaaban, S.; Davies, C.; Waldmann, H. Eur. J. Org. Chem. 2020, 2020, 6512.
[5]	Yan, X.; Jiang, J.; Wang, J. Angew. Chem., Int. Ed. 2022, 61, e202201522.
[6]	Wang, S. G.; Park, S. H.; Cramer, N. Angew. Chem., Int. Ed. 2018, 57, 5459.
[7]	(a) Wang, S.-G.; Cramer, N. ACS Catal. 2020, 10, 8231. pmid: 29732080
	(b) Cui, W. J.; Wu, Z. J.; Gu, Q.; You, S. L. J. Am. Chem. Soc. 2020, 142, 7379. pmid: 29732080
	(c) Sun, Y.; Cramer, N. Chem. Sci. 2018, 9, 2981. doi: 10.1039/c7sc05411d pmid: 29732080
	(d) Ye, B.; Cramer, N. J. Am. Chem. Soc. 2013, 135, 636. pmid: 29732080
[8]	Duchemin, C.; Smits, G.; Cramer, N. Organometallics 2019, 38, 3939. doi: 10.1021/acs.organomet.9b00365
[9]	Zheng, J.; Cui, W. J.; Zheng, C.; You, S. L. J. Am. Chem. Soc. 2016, 138, 5242. doi: 10.1021/jacs.6b02302 pmid: 27070297
[10]	Pan, C.; Yin, S. Y.; Wang, S. B.; Gu, Q.; You, S. L. Angew. Chem., Int. Ed. 2021, 60, 15510.
[11]	Li, G.; Yan, X.; Jiang, J.; Liang, H.; Zhou, C.; Wang, J. Angew. Chem., Int. Ed. 2020, 59, 22436.
[12]	Liang, H.; Vasamsetty, L.; Li, T.; Jiang, J.; Pang, X.; Wang, J. Chem.-Eur. J. 2020, 26, 14546.
[13]	(a) Yang, H.; Zhang, R.; Zhang, S.-Z.; Gu, Q.; You, S.-L. ACS Catal. 2023, 13, 8838.
	(b) Guo, W.; Pang, X.; Jiang, J.; Wang, J. Org. Lett. 2023, 25, 3823.
[14]	Guo, W.; Jiang, J.; Wang, J. Angew. Chem., Int. Ed. 2024, 63, e202400279.
[15]	Jia, Z. J.; Merten, C.; Gontla, R.; Daniliuc, C. G.; Antonchick, A. P.; Waldmann, H. Angew. Chem., Int. Ed. 2017, 56, 2429.
[16]	Pototskiy, R. A.; Kolos, A. V.; Nelyubina, Y. V.; Perekalin, D. S. Eur. J. Org. Chem. 2020, 2020, 6019.
[17]	Kharitonov, V. B.; Podyacheva, E.; Chusov, D.; Nelyubina, Y. V.; Muratov, D. V.; Loginov, D. A. Org. Lett. 2023, 25, 8906. doi: 10.1021/acs.orglett.3c03726 pmid: 38051945
[18]	Edlová, T.; Rybáček, J.; Cattey, H.; Vacek, J.; Bednárová, L.; Gendre, P. L.; Normand, A. T.; Stará, I. G.; Starý, I. Angew. Chem., nt. Ed. 2024, 63, e202414698.
[19]	Trifonova, E. A.; Ankudinov, N. M.; Mikhaylov, A. A.; Chusov, D. A.; Nelyubina, Y. V.; Perekalin, D. S. Angew. Chem., Int. Ed. 2018, 57, 7714.
[20]	Kolos, A. V.; Nelyubina, Y. V.; Sundararaju, B.; Perekalin, D. S. Organometallics 2021, 40, 3712.
[21]	Farr, C. M. B.; Kazerouni, A. M.; Park, B.; Poff, C. D.; Won, J.; Sharp, K. R.; Baik, M.-H.; Blakey, S. B. J. Am. Chem. Soc. 2020, 142, 13996.
[22]	Zhang, C.; Jiang, J.; Huang, X.; Wang, J. ACS Catal. 2023, 13, 10468.
[23]	Kolos, A. V.; Nelyubina, Y. V.; Podyacheva, E. S.; Perekalin, D. S. Dalton Trans. 2023, 52, 17005.
[24]	Gross, P.; Im, H.; Laws, D., III; Park, B.; Baik, M.-H.; Blakey, S. B. J. Am. Chem. Soc. 2024, 146, 1447.

不含手性取代基的平面手性环戊二烯基铑催化剂在不对称碳氢键活化中的应用