Doubly Switchable Diastereodivergent Strategy Mediated by a Chiral Sulfoxide to Access Disubstituted Tetrahydrocyclopenta­pyranone and Hexahydrocyclopentapyranol Scaffolds via Nazarov Cyclization

Erwann Grenet; Arie van der Lee; Xavier J. Salom-Roig

doi:10.1055/a-1983-2140

Synthesis, Table of Contents

Synthesis 2023; 55(04): 580-597
DOI: 10.1055/a-1983-2140

feature

Doubly Switchable Diastereodivergent Strategy Mediated by a Chiral Sulfoxide to Access Disubstituted Tetrahydrocyclopentapyranone and Hexahydrocyclopentapyranol Scaffolds via Nazarov Cyclization

Authors

Erwann Grenet

^aInstitut des Biomolécules Max Mousseron, Université de Montpellier, CNRS, ENSCM, 1019, route de Mende, 34293 Montpellier, France
Arie van der Lee

^bIEM, Université de Montpellier, CNRS, ENSCM, Place Eugène Bataillon, 34095 Montpellier, France
Xavier J. Salom-Roig∗

^aInstitut des Biomolécules Max Mousseron, Université de Montpellier, CNRS, ENSCM, 1019, route de Mende, 34293 Montpellier, France

Abstract

All articles of this category

Abstract

Activated dienones bearing a chiral sulfoxide were transformed diastereodivergently into the corresponding disubstituted 3,4,5,6-tetrahydrocyclopenta[b]pyran-7(2H)-ones. The torquoselectivity of the reaction could be switched by changing the Lewis acid used as promoter. From the four possible stereoisomers, only the two trans were observed. In a second switchable diastereodivergent step, both corresponding diastereomeric 2,3,4,5,6,7-hexahydrocyclopenta[b]pyran-7-ols were obtained via the diastereoselective reduction of the ketone by changing the reducing agent. The Lewis acids as well as the reducing agents employed in both diastereodivergent steps were achiral, the diastereoselectivities being dictated by the sulfinyl auxiliary.

Key words

asymmetric synthesis - chiral auxiliaries - cyclization - diastereoselectivity - stereoselective synthesis

Full Text

References

References
1 Calcaterra A, D’Acquarica I. J. Pharm. Biomed. Anal. 2018; 147: 323
2 Lin L, Feng X. Chem. Eur. J. 2017; 23: 6464

3a Grenet E, Martinez J, Salom-Roig XJ. Chem. Eur. J. 2016; 22: 16770
3b Grenet E, Robidas R, va der Lee A, Legault CY, Salom-Roig XJ. Eur J. Org. Chem. 2022; e202200828

4a Qi Q.-Y, Bao L, Ren J.-W, Han J.-J, Zhang Z.-Y, Li Y, Yao Y.-J, Cao R, Liu H.-W. Org. Lett. 2014; 16: 5092
4b Qi Q.-Y, Ren J.-W, Sun L.-W, He L.-W, Bao L, Yue W, Sun Q.-M, Yao Y.-J, Yin W.-B, Liu H.-W. Org. Lett. 2015; 17: 3098
4c Qiu Y, Lan W.-J, Li H.-J, Chen L.-P. Molecules 2018; 23: 2095

5 Bhattacharya C, Bonfante P, Deagostino A, Kapulnik Y, Larini P, Occhiato EG, Prandi C, Venturello P. Org. Biomol. Chem. 2009; 7: 3413

6a Hubbs JL, Fuller NO, Austin WF, Shen R, Creaser SP, McKee TD, Loureiro RM. B, Tate B, Xia W, Ives J, Bronk BS. J. Med. Chem. 2012; 55: 9270
6b Findeis MA, Schroeder F, McKee TD, Yager D, Fraering PC, Creaser SP, Austin WF, Clardy J, Wang R, Selkoe D, Eckman CB. ACS Chem. Neurosci. 2012; 3: 941
6c Fuller NO, Hubbs JL, Austin WF, Creaser SP, McKee TD, Loureiro RM. B, Tate B, Xia W, Ives JL, Findeis MA, Bronk BS. ACS Med. Chem. Lett. 2012; 3: 908

7 Su Y, Wua L, Muc G, Wang Q, Yang B, Cheng G, Kuang H. Bioorg. Med. Chem. 2017; 25: 4917
8 For an overview on the latest applications of chiral sulfoxides in asymmetric synthesis, see: Carreño MC, Hernández-Torres G, Ribagorda M, Urbano A. Chem. Commun. 2009; 6129

9a Bauder C, Martinez J, Salom-Roig XJ. Curr. Org. Synth. 2013; 10: 885
9b Tang Y, Sun Y, Liu J, Duttwyler S. Org. Biomol. Chem. 2016; 14: 5580

10a Fernández de la Pradilla R, Lwoff N, del Aguila MA, Tortosa M, Viso A. J. Org. Chem. 2008; 73: 8929
10b Simal C, Bates RH, Ureña M, Giménez I, Koutsou C, Infantes L, Fernández de la Pradilla R, Viso A. J. Org. Chem. 2015; 80: 7674

11 Kingsbury CA, Draney D, Sopchik A, Rissler W, Durham D. J. Org. Chem. 1976; 41: 3863
12 CCDC 2176273 (13a), 1487502 (1b) and 1487499 (21) contain the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures
13 For the pioneering use of AlCl₃ as a catalyst for a Nazarov reaction, see: Liang G, Gradl SN, Trauner D. Org. Lett. 2003; 5: 4931
14 Canterbury DP, Herrick IR, Um J, Houk KN, Frontier AJ. Tetrahedron 2009; 65: 3165

15a Russell GA, Mikol GJ. J. Am. Chem. Soc. 1966; 88: 5498
15b Holton RA, Crouse DJ, Williams AD, Kennedy RM. J. Org. Chem. 1987; 52: 2317

16a Solladié G, Greck C, Demailly G, Solladié-Cavallo A. Tetrahedron Lett. 1982; 23: 5047
16b Solladié G, Demailly G, Greck C. Tetrahedron Lett. 1985; 25: 435

17 Kosugi H, Konta H, Uda H. J. Chem. Soc., Chem. Commun. 1985; 211

18a García Ruano JL, Maestro MC, Sánchez-Sancho F. Tetrahedron: Asymmetry 1995; 6: 2299
18b García Ruano JL, Maestro MC, Barros D, González-Vadillo AM. Tetrahedron: Asymmetry 1996; 7: 1819
18c García Ruano JL, Yuste F, Sánchez-Obregón R, Carrasco A, Peralta M, Quintero L, Walls F. Tetrahedron: Asymmetry 2000; 11: 3079
18d Carreño MC, Sanz-Cuesta MJ, Colobert F, Solladié G. Org. Lett. 2004; 6: 3537

19 Bonner WA. J. Am. Chem. Soc. 1952; 74: 1033
20 Rueping M, Ieawsuwan W, Antonchick AP, Nachtsheim BJ. Angew. Chem. Int. Ed. 2007; 46: 2097 ; Angew. Chem. 2007, 119, 2143
21 He W, Herrick IR, Atesin TA, Caruana PA, Kellenberger CA, Frontier AJ. J. Am. Chem. Soc. 2008; 130: 1003
22 White TD, West FG. Tetrahedron Lett. 2005; 46: 5629

Supplementary Material

Supporting Information (PDF)

Doubly Switchable Diastereodivergent Strategy Mediated by a Chiral Sulfoxide to Access Disubstituted Tetrahydrocyclopenta­pyranone and Hexahydrocyclopentapyranol Scaffolds via Nazarov Cyclization

Authors

Doubly Switchable Diastereodivergent Strategy Mediated by a Chiral Sulfoxide to Access Disubstituted Tetrahydrocyclopentapyranone and Hexahydrocyclopentapyranol Scaffolds via Nazarov Cyclization