Rhodium-Catalyzed Enal Transfer Reactions of Diazoenals: Application to Diastereoselective Synthesis of Dienal-Cyclopropanes

Kamakshya Prasad Mahata; Sudhir Muduli; Sreenivas Katukojvala

doi:10.1055/a-2746-2709

Synlett, Table of Contents

Synlett
DOI: 10.1055/a-2746-2709

Letter

Published as part of the Special Issue dedicated to Prof. S. Chandrasekaran on his 80th birthday

Rhodium-Catalyzed Enal Transfer Reactions of Diazoenals: Application to Diastereoselective Synthesis of Dienal-Cyclopropanes

Authors

Kamakshya Prasad Mahata

¹Department of Chemistry, Indian Institute of Science Education and Research Bhopal, Bhopal, India (Ringgold ID: RIN189785)
Sudhir Muduli

¹Department of Chemistry, Indian Institute of Science Education and Research Bhopal, Bhopal, India (Ringgold ID: RIN189785)
Sreenivas Katukojvala

¹Department of Chemistry, Indian Institute of Science Education and Research Bhopal, Bhopal, India (Ringgold ID: RIN189785)

Abstract

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Dedication

This work is dedicated to Professor S. Chandrasekaran on the occasion of his 80th birthday

Abstract

Vinyl cyclopropanes are valuable functional groups in drugs or natural products as well as established precursors to trigger a rich variety of synthetic transformations. However, their reactive nature makes their installation challenging. We herein present a modular access to highly diastereoselective (>20:1) dienal-cyclopropanes from rhodium-enalcarbenoids and styrenes under mild conditions. This protocol was extended to synthesize a biologically relevant substituted pyrroline scaffold. Overall, this Rh (II)-catalyzed cyclopropanation exhibits good functional group tolerance, facile scalability, and selective access to a diverse range of dienal cyclopropane motifs featuring an all-carbon ε-quaternary stereocenter.

Keywords

Cyclopropanes - Dienalcarbenoids - Diazo compounds

Full Text

References

References

1a Salaün J. In: Small Ring Compounds in Organic Synthesis VI. de Meijere A. ed. Vol. 207. Berlin: Springer; 2000: 1-67
1b Chen DYK, Pouwer RH, Richard J-A. Chem Soc Rev 2012; 41: 4631-4642
1c Talele TT. J Med Chem 2016; 59: 8712-8756
1d Fan Y-Y, Gao X-H, Yue J-M. Sci China Chem 2016; 59: 1126-1141
1e Ebner C, Carreira EM. Chem Rev 2017; 117: 11651-11679

2a Chen H, Zhang Z, Wang L. et al. Medicine 2020; 99: e23357
2b Zhang Z, Wang S, Tu X. et al. J Med Virol 2020; 92: 2631-2636

3 Krause J. Microorganisms 2024; 12: 1445
4 Vuligonda V, Thacher SM, Chandraratna RAS. J Med Chem 2001; 44: 2298-2303

5a Lybrand DB, Xu H, Last RL, Pichersky E. Trends Plant Sci 2020; 25: 1240-1251
5b Ravula AR, Yenugu S. Crit Rev Toxicol 2021; 51: 117-140
5c Hodosan C, Gird CE, Ghica MV. et al. Plants 2023; 12: 4022

6a Faust R. Angew Chem Int Ed 2001; 40: 2251-2253
6b Hiratsuka T, Suzuki H, Minami A, Oikawa H. Org Biomol Chem 2017; 15: 1076-1079

7a Nachimuthu K, Nallasivam JL. Org Biomol Chem 2024; 22: 4212-4242
7b Schneider TF, Kaschel J, Werz DB. Angew Chem Int Ed 2014; 53: 5504-5523
7c Rubin M, Rubina M, Gevorgyan V. Chem Rev 2007; 107: 3117-3179
7d Meazza M, Guo H, Rios R. Org Biomol Chem 2017; 15: 2479-2490

Selected ring opening reaction of VCP, see:

8a Fumagalli G, Stanton S, Bower JF. Chem Rev 2017; 117: 9404-9432
8b Wang J, Dai Z, Xiong C, Zhu J, Lu J, Zhou Q. Adv Synth Catal 2019; 361: 5105-5111
8c Wang J, Blaszczyk SA, Li X, Tang W. Chem Rev 2021; 121: 110-139
8d Chen P, Huang P-F, Xiong B-Q, Huang H-W, Tang K-W, Liu Y. Org Lett 2022; 24: 5726-5730

Selected cycloaddition reaction of VCP, see:

9a Yang J, Zhang P, Shen Z, Zhou Y, Yu Z-X. Chem 2003; 9: 1477-1494
9b Wang Y, Yu Z-X. Acc Chem Res 2015; 48: 2288-2296
9c Li M-M, Xiong Q, Qu B-L. et al. Angew Chem 2020; 132: 17582-17587

Selected rearrangement reaction of VCP, see:

10a Houk KN, Nendel M, Wiest O, Storer JW. J Am Chem Soc 1997; 119: 10545-10546
10b Hudlicky T, Reed JW. Angew Chem Int Ed 2010; 49: 4864-4876
10c Hudlicky T, Reed JW. Angew Chem 2010; 122: 4982-4994
10d Krüger S, Gaich T. Beilstein J OrgChem 2014; 10: 163-193
10e Wu J, Tang YH, Wei W. et al. Angew Chem Int Ed 2018; 57: 6284-6288

11 Ganesh V, Chandrasekaran S. Synthesis 2016; 48: 4347-4380
12 Bruffaerts J, Pierrot D, Marek I. Nat Chem 2018; 10: 1164-1170

Reviews on synthesis of VCP, see:

13a Li AH, Dai LX, Aggarwal VK. Chem Rev 1997; 97: 2341-2372
13b Hodgson DM, Pierard FYTM, Stupple PA. Chem Soc Rev 2001; 30: 50-61
13c Maas G. Chem Soc Rev 2004; 33: 183-190
13d Qian D, Zhang J. Chem Soc Rev 2015; 44: 677-698
13e Dian L, Marek I. Chem Rev 2018; 118: 8415-8434
13f Cohenand Y, Marek I. Acc Chem Res 2022; 55: 2848-2868

Recent works on synthesis of VCP, see

14a Yang Y, Liu Z, Song Q. et al. Chem Catal 2022; 2: 563-577
14b Mendel M, Gnagi L, Dabranskaya U, Schoenebeck F. Angew Chem Int Ed 2023; 62: e202211167
14c Cao B, Liu G, Huang Z. ACS Catal 2024; 14: 12846-12856
14d Xie X, Zhao Z, Wang J, Li SW. Org Lett 2024; 26: 8144-8148
14e Deshwal S, Gopalakrishnan DK, Purohit A, Karmakar T, Vaitla J. Org Biomol Chem 2024; 22: 6294-6307
14f Gong Y, Xu X-C, Meng Y-X, Zhao Y-L. Org Chem Front 2025; 12: 3011-3017

15 Chennamsetti H, Rathore KS, Chatterjee S, Mandal PK, Katukojvala S. JACS Au 2024; 4: 2099-2107
16 Rathore KS, Katukojvala S. Tetrahedron Lett 2014; 55: 6370
17 Doyle MP, Duffy R, Ratnikov M, Zhou L. Chem Rev 2010; 110: 704-724
18 Hansen JH, Gregg TM, Ovalles SR, Lian Y, Autschbach J, Davies HML. J Am Chem Soc 2011; 133: 5076-5085

19a Smolanoff J, Kluge AF, Meinwald J. et al. Science 1975; 188: 734-736
19b Nakashima T, Miyano R, Iwatsuki M. et al. J Antibiot 2016; 69: 611-615

20 Doyle MP, McKervey MA, Ye T. Modern Catalytic Methods for Organic Synthesis with Diazo Compounds. New York: Wiley; 1998

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