Construction of Vicinal Stereocenters via Asymmetric Cyanosilylation

Abstract

Asymmetric cyanosilylation serves as an important tool to convert easily available ketones into cyanohydrins of diverse reactivity. Whereas a large library of organocatalysts and transition-metal catalysts have been identified for monoketones, cyanosilylation of more-complex substrates, particularly those giving enantioenriched vicinal stereocenters, is underexplored in comparison. Here, a pair of recently published kinetic resolution and desymmetrization methods are highlighted for their success in constructing complex vicinal stereocenters by cyanosilylation using tailored aluminum and magnesium catalysts, respectively.

1 Introduction

2 Kinetic Resolution of α-Branched Ketones

3 Desymmetrization of 1,3-Diketones

4 Conclusion

Key words

cyanosilylation - asymmetric catalysis - vicinal stereocenters - quaternary stereocenters - kinetic resolution - desymmetrization

Publication History

Received: 09 August 2023

Accepted after revision: 25 August 2023

Accepted Manuscript online:
25 August 2023

Article published online:
05 October 2023

• References

• 1 Lovering F, Bikker J, Humblet C. J. Med. Chem. 2009; 52: 6752
• 2 Lovering F. MedChemComm 2013; 4: 515

For selected reviews, see:
• 3a Long R, Huang J, Gong J, Yang Z. Nat. Prod. Rep. 2015; 32: 1584
• 3b Büschleb M, Dorich S, Hanessian S, Tao D, Schenthal KB, Overman LE. Angew. Chem. Int. Ed. 2016; 55: 4156
• 3c Zhou F, Zhu L, Pan B.-W, Shi Y, Liu Y.-L, Zhou J. Chem. Sci. 2020; 11: 9341

For selected reviews of cyanosilylation of ketones, see:
• 4a Brunel J.-M, Holmes IP. Angew. Chem. Int. Ed. 2004; 43: 2752
• 4b North M, Usanov DL, Young C. Chem. Rev. 2008; 108: 5146
• 4c Kurono N, Ohkuma T. ACS Catal. 2016; 6: 989
• 4d Pahar S, Kundu G, Sen SS. ACS Omega 2020; 5: 25477
• 4e Wu W.-B, Yu J.-S, Zhou J. ACS Catal. 2020; 10: 7668
• 5 Wu W.-B, Yu X, Yu J.-S, Wang X, Wang W.-G, Zhou J. CCS Chem. 2022; 4: 2140

For selected examples, see:
• 6a Zeng X.-P, Cao Z.-Y, Wang X, Chen L, Zhou F, Zhu F, Wang C.-H, Zhou J. J. Am. Chem. Soc. 2016; 138: 416
• 6b Zeng X.-P, Zhou J. J. Am. Chem. Soc. 2016; 138: 8730
• 7 Xu P, Shen C, Xu A, Low K.-H, Huang Z. Angew. Chem. Int. Ed. 2022; 61: e202208443

For selected examples, see:
• 8a Xu P, Huang Z. Nat. Chem. 2021; 13: 634
• 8b Zheng Y, Zhang S, Low K.-H, Zi W, Huang Z. J. Am. Chem. Soc. 2022; 144: 1951
• 8c Xu P, Liu S, Huang Z. J. Am. Chem. Soc. 2022; 144: 6918
• 8d Liu H, Lau HM, Xu P, Chan TH, Huang Z. Nat. Commun. 2022; 13: 4759