Design and Synthesis of Out/Out, Out/In, and In/In Epoxides in Polycyclic Cage Frameworks

Sambasivarao Kotha; Mohammad Salman

doi:10.1055/a-2384-6736

Synlett, Table of Contents

Synlett 2024; 35(20): 2441-2446
DOI: 10.1055/a-2384-6736

letter

Special Issue to Celebrate the 75th Birthday of Prof. B. C. Ranu

Design and Synthesis of Out/Out, Out/In, and In/In Epoxides in Polycyclic Cage Frameworks

Sambasivarao Kotha∗

^aDepartment of Chemistry, Indian Institute of Technology-Bombay, Powai, 400076, India

^bDepartment of Chemistry, Sunandan Divatia School of Science, SVKM’s NMIMS (Deemed-to-be) University, Vile Parle (West), Mumbai, 400056, India

,

Mohammad Salman

^aDepartment of Chemistry, Indian Institute of Technology-Bombay, Powai, 400076, India

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Abstract

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Abstract

We report a useful synthetic approach to assemble in/in epoxide, in/out epoxide, and out/out epoxide in cage systems using the Corey–Chaykovsky reaction and the Peterson olefination as key steps. In this regard, a variety of pentacycloundecane (PCUD) based cage compounds containing oxirane rings with diverse stereochemical disposition were synthesized via a simple synthetic sequence. Five cage diones were used for this purpose, and the starting cage diones were prepared with easily accessible starting materials such as 1,4-hydroquinone derivatives and cyclopentadiene. Here, we have used the Diels–Alder (DA) reaction, a [2+2] photocycloaddition, the Corey–Chaykovsky reaction, and the Peterson olefination as crucial steps to prepare the target molecules.

Key words

Diels–Alder reaction - photocycloaddition - cage compounds - PCUD - Peterson olefination - Corey–Chaykovsky reaction - m-CPBA oxidation

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References

References

1a Marchand AP. Aldrichim. Acta 1995; 28: 95
1b Marchand AP, Kaya R. J. Org. Chem. 1983; 48: 5392

2 Marchand AP. Synlett 1991; 73
3 Upadhayaya RS, Jain S, Sinha N, Kishore N, Chandra R, Arora SK. Eur. J. Med. Chem. 2004; 39: 579

4a Lebouvier N, Giraud F, Corbin T, Na YM, Le Baut G, Marchand AP, Le Borgne M. Tetrahedron Lett. 2006; 47: 6479
4b Eicher T, Hauptmann S. The Chemistry of Heterocycles . Wiley-VCH; Weinheim: 2005: 17-23

5 Simmons HE, Park CH. J. Am. Chem. Soc. 1968; 90: 2428
6 Park CH, Simmons HE. J. Am. Chem. Soc. 1968; 90: 2429
7 Park CH, Simmons HE. J. Am. Chem. Soc. 1968; 90: 2431
8 Simmons HE, Park CH, Uyeda RT, Habibi MF. Trans. N.Y. Acad. Sci. Ser. II 1970; 32: 521
9 Dietrich B, Lehn J.-M, Sauvage JP. Tetrahedron Lett. 1969; 10: 2885
10 Dietrich B, Lehn J.-M, Sauvage JP, Blanzat J. Tetrahedron 1973; 29: 1629
11 Dietrich B, Lehn J.-M, Sauvage JP. Tetrahedron 1973; 29: 1647
12 Lehn J.-M. Struct. Bond. 1973; 16: 1
13 Lehn J.-M. Acc. Chem. Res. 1978; 11: 49
14 Lehn J.-M. Science 1985; 227: 849
15 Lehn J.-M. Angew. Chem., Int. Ed. Engl. 1988; 27: 89
16 Lehn J.-M. Chem. Scr. 1988; 28: 237

17a McMurry JE, Hodge CN. J. Am. Chem. Soc. 1984; 106: 6450
17b McMurry JE, Lectka T, Hodge CN. J. Am. Chem. Soc. 1989; 111: 8867

18 McMurry JE, Lectka T. J. Am. Chem. Soc. 1993; 115: 10167
19 Hopf H. Classics in Hydrocarbon Chemistry . Wiley-VCH; Weinheim: 2000: 98
20 Mehta G, Srikrishna A, Reddy AV, Nair MS. Tetrahedron 1981; 37: 4543
21 Mehta G, Rao KS. Tetrahedron Lett. 1983; 24: 809

22a Mehta G, Reddy DS, Murty AN. J. Chem. Soc. 1983; 824
22b Kotha S, Meshram M. ChemCatChem 2020; 12: 6131

23 Marchand AP, Chou T.-C. J. Chem. Soc., Perkin Trans. 1 1973; 1948
24 Marchand AP, Allen RW. J. Org. Chem. 1974; 39: 1596
25 Marchand AP, Chou T.-C. Tetrahedron 1975; 31: 2655
26 Marchand AP, Chou T.-C. Tetrahedron Lett. 1975; 3359
27 Marchand AP, Chou T.-C, Ekstrand JD, van der HelmD. J. Org. Chem. 1976; 41: 1438
28 Marchand AP, Suri SC, Earlywine AD, Powell DR, van der HelmD. J. Org. Chem. 1984; 49: 670

29a Paquette LA, Ternansky RJ, Balogh DW, Kentgen G. J. Am. Chem. Soc. 1983; 105: 5446
29b Osawa E, Rudzinski JM, Xun Y.-M. Struct. Chem. 1990; 1: 333
29c Fessner W-D, Sedelmeier G, Spurr PR, Rihs G, Prinzbach H. J. Am. Chem. Soc. 1987; 109: 4626
29d Kent GJ, Godleski SA, Osawa E, Schleyer P. vR. J. Org. Chem. 1977; 42: 3852
29e Schleyer P. vR. J. Am. Chem. Soc. 1957; 79: 3292
29f Cookson RC, Grundwell E, Hudec J. Chem Ind. 1958; 1003
29g Marchand AP. Chemistry of Pentacyclo [5.4.0.0^2,6.0^3,10.0^5,9]undecane (PCUD) and Related Systems. In Advances in Theoretically Interesting Molecules, Vol. 1. Thummel RP. JAI Press; Connecticut: 1989: 357

30 Gaidai AV, Volochnyuk DM, Shishkin OV, Fokin AA, Levandovskiy IA. Synthesis 2012; 44: 810
31 Chan TH, Chang E. J. Org. Chem. 1974; 39: 3264

32a Hsu LF, Chang CP, Li MC. J. Org. Chem. 1993; 58: 4756
32b Homologation Reactions, Vol. 1 . Pace V. Wiley-VCH; Weinheim: 2023
32c Homologation Reactions, Vol. 2 . Pace V. Wiley-VCH; Weinheim: 2023

33 Trost BM, Latimer HL. J. Org. Chem. 1978; 43: 1031
34 Marchand AP, Rajapaksa D, Vidyasagar V, Watson WH, Kashyap RP. Synth. Commun. 1996; 26: 819
35 Tirado-Rives J, Jorgensen WL. J. Chem. Theory Comput. 2008; 4: 297
36 Davidson ER, Feller D. Chem. Rev. 1986; 86: 681

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