Download PDF
Synlett
DOI: 10.1055/a-2356-8408
letter
Special Issue to Celebrate the 75th Birthday of Prof. B. C. Ranu

Synthesis and Reactions of Pentacycloundecane Derivatives Related to Cookson’s Dione

Sambasivarao Kotha∗
a   Department of Chemistry, Indian Institute of Technology-Bombay, Powai, 400076, India
b   Department of Chemistry, Sunandan Divatia School of Science, SVKM’s NMIMS (Deemed-to-be) University, Vile Parle (West), Mumbai, 400056, India
,
Mohammad Salman
a   Department of Chemistry, Indian Institute of Technology-Bombay, Powai, 400076, India
› Author AffiliationsM.S. thanks the University Grants Commission (UGC), New Delhi, for the award of a research fellowship.
› Further Information
    Permissions and Reprints All articles of this category


Abstract

In this study, a pentacyclic keto-olefin was treated with thallium(III) nitrate trihydrate, resulting in the formation of mono ring-expanded product. However, when the corresponding dialkene was treated with thallium(III) nitrate trihydrate, an unexpected ring-closure product was obtained instead of the expected double ring-expanded product. The use of the Tebbe reagent facilitated the olefination of hindered and enolizable cage dione derivatives, converting both keto moieties into methylene groups and forming the desired diolefin. Notably, conventional Wittig reagents proved to be ineffective in the olefination sequence with cage diones.

Key words

Diels–Alder reaction - photocycloaddition - pentacycloundecanes - Peterson reaction - thallium trinitrate - ring expansion

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-2356-8408.
  • Supporting Information


Publication History

Received: 25 May 2024

Accepted after revision: 12 June 2024

Accepted Manuscript online:
28 June 2024

Article published online:
17 July 2024

© 2024. Thieme. All rights reserved

Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany

 

  • References and Notes

  • 1 Schleyer P. von R. J. Am. Chem. Soc. 1957; 79: 3292
    • 2a Onajole OK, Govender K, Govender P, van Helden PD, Kruger HG, Maguire GE. M, Muthusamy K, Pillay M, Wiid I, Govender T. Eur. J. Med. Chem. 2009; 44: 4297
    • 2b Rey-Carrizo M, Barniol-Xicota M, Ma C, Frigolé-Vivas M, Torres E, Naesens L, Llabrés S, Juárez-Jiménez J, Luque FJ, DeGrado WF, Lamb RA, Pinto LH, Vázquez S. J. Med. Chem. 2014; 57: 5738
    • 3a Michalson ET, Szmuszkovics J. Prog. Drug Res. 1989; 33: 135
    • 3b Joubert J, Geldenhuys WJ, Van der Schyf CJ, Oliver DW, Kruger HG, Govender T, Malan SF. ChemMedChem 2012; 7: 375
    • 3c Gante J. Angew. Chem. Int. Ed. 1994; 33: 1699
    • 3d Govender T, Kruger HG, Makatini M, Onajole OK. Struct. Chem. 2008; 19: 719
    • 4a Marchand AP, Dave PR, Rajapaksa D, Arney BE. Jr, Flippen-Anderson JL, Gilardi R, George C. J. Org. Chem. 1989; 54: 1769
    • 4b Marchand AP, Arney BE. Jr, Dave PR. J. Org. Chem. 1988; 53: 443
    • 4c Lal S, Mallick L, Rajkumar S, Oommen OP, Reshmi S, Kumbhakarna N, Chowdhury A, Namboothiri IN. N. J. Mater. Chem. A 2015; 3: 22118
  • 5 Kaszynski P, Friedli AC, Michl J. J. Am. Chem. Soc. 1992; 114: 601
    • 6a Hattori Y, Miyajima T, Sakai M, Nagase Y, Nemoto N. Polymer 2008; 49: 2825
    • 6b Khardin AP, Radchenko SS. Russ. Chem. Rev. 1982; 51: 272
    • 7a Bartsch RA, Eley M, Marchand AP, Shukla R, Kumar KA, Reddy GM. Tetrahedron 1996; 52: 8979
    • 7b Williams SM, Brodbelt JS, Marchand AP, Cal D, Mlinaric-Majerski K. Anal. Chem. 2002; 74: 4423
    • 7c Marchand AP, Chong HS, Ganguly B. Tetrahedron: Asymmetry 1999; 10: 4695
    • 7d Hayakawa K, Kido K, Kanematsu K. J. Chem. Soc., Chem. Commun. 1986; 268
    • 7e Kotha S. Tetrahedron 1994; 50: 3639
    • 8a Katz TJ, Acton N. J. Am. Chem. Soc. 1973; 95: 2738
    • 8b Griesbeck AG, Deufel T, Hohlneicher G, Rebentisch R, Steinwascher J. Eur. J. Org. Chem. 1998; 1998: 1759
    • 9a Osawa E, Yonemitsu O. Carbocyclic Caged Compounds: Chemistry and Applications. VCH; New York: 1992
      Google Scholar
    • 9b Cage Hydrocarbons . Olah GA. Wiley-Interscience; New York: 1990
      Google Scholar
    • 9c Marchand AP. Adv. Theor. Interesting Mol. 1989; 1: 357
    • 9d Kotha S, Cheekatla S. J. Org. Chem. 2018; 83: 6315
  • 10 Mehta G, Srikrishna A. Chem. Rev. 1997; 97: 671
  • 11 Teransky RJ, Balogh DW, Paquette LA. J. Am. Chem. Soc. 1982; 104: 4503
  • 12 Levandovsky IA, Sharapa DI, Cherenkova OA, Gaidai AV, Shubina TE. Russ. Chem. Rev. 2010; 79: 1005
  • 13 Fessner W.-D, Prinzbach H, Rihs G. Tetrahedron Lett. 1983; 24: 5857
  • 14 Bizzini LD, Müntener T, Häussinger D, Neuburger M, Mayor M. Chem. Commun. 2017; 53: 11399
  • 15 Hargittai I, Brunvoll J, Cyvin SJ, Marchand AP. J. Mol. Struct. 1986; 140: 219
    • 16a Cookson RC, Hill RR, Hudec J. J. Chem. Soc. 1964; 3043
    • 16b Geldenhuys WJ, Malan SF, Murugesan T, Van der Schyf CJ, Bloomquist JR. Bioorg. Med. Chem. 2004; 12: 1799
    • 16c Kotha S, Cheekatla SR, Meshram M. ChemCatChem 2020; 12: 6131
    • 16d Kotha S, Mehta G. J. Org. Chem. 2023; 88: 11650
    • 17a Okamoto Y, Senokuchi K, Kanematsu K. Chem. Pharm. Bull. 1984; 32: 4593
    • 17b Eaton PE, Cole TW. J. Am. Chem. Soc. 1964; 86: 3157
    • 17c Marchand AP, Sharma GV. M, Annapurna GS, Pednekar PR. J. Org. Chem. 1987; 52: 4784
    • 17d Bisetty K, Govender T, Kruger HG. Biopolymers 2006; 81: 339
    • 17e Oliver DW, Dekker TG, Snyckers FO. Arzneim. Forsch. 1991; 41: 549
    • 17f Oliver DW, Dekker TG, Snyckers FO. Eur. J. Med. Chem. 1991; 26: 375
    • 17g Banister SD, Manoli M, Barron ML, Werry EL, Kassiou M. Bioorg. Med. Chem. 2013; 21: 6038
    • 17h Banister SD, Moussa IA, Beinat C, Reynolds AJ, Schiavini P, Jorgensen WT, Kassiou M. Bioorg. Med. Chem. Lett. 2011; 21: 38
    • 17i James B, Viji S, Mathew S, Nair MS, Lakshmanan D, Kumar RA. Tetrahedron Lett. 2007; 48: 6204
    • 18a Fukunaga T, Clement RA. J. Org. Chem. 1977; 42: 270
    • 18b Dauben WG, Schallhorn CH, Whalen DL. J. Am. Chem. Soc. 1971; 93: 1446
    • 18c Alifantes J, Lapis AA. M, Martins JE. D, Costa VE. U. J. Chem. Soc., Perkin Trans. 2 2001: 7
    • 18d Nair MS, Sudhir U, Joly S, Rath NP. Tetrahedron 1999; 55: 7653
    • 18e Chow TJ, Wu TK. J. Org. Chem. 1991; 56: 6833
    • 18f Majerski Z, Veljkovic J, Kaselj M. J. Org. Chem. 1988; 53: 2662
    • 18g Kent GJ, Godleski SA, Osawa E, Schleyer P. vonR. J. Org. Chem. 1977; 42: 3852
    • 18h Gutierrez O, Aubé J, Tantillo DJ. J. Org. Chem. 2012; 77: 640
    • 19a Marchand AP, Reddy SP, Rajapaksa D, Ren CT, Watson WH, Kashyap RP. J. Org. Chem. 1990; 55: 3493
    • 19b Mehta G, Rao KS. J. Org. Chem. 1985; 50: 5537
    • 19c Coxon JM, Fong ST, Steel PJ. Tetrahedron Lett. 1990; 31: 7479
    • 19d Marchand AP, Reddy GM, Watson WH, Nagl A. J. Org. Chem. 1988; 53: 5969
  • 20 Onajole OK, Coovadia Y, Kruger HG, Maguire GE. M, Pillay M, Govender T. Eur. J. Med. Chem. 2012; 54: 1
  • 21 Wanka L, Iqbal K, Schreiner PR. Chem. Rev. 2013; 113: 3516
    • 22a Wilkinson SM, Gunosewoyo H, Barron ML, Boucher A, McDonnell M, Turner P, Morrison DE, Bennett MR, McGregor IS, Rendina LM, Kassiou M. ACS Chem. Neurosci. 2014; 5: 335
    • 22b Oliver DW, Dekker TG, Snyckers FO, Fourie TG. J. Med. Chem. 1991; 34: 851
  • 23 Paquette LA, Fischer JW, Engel P. J. Org. Chem. 1985; 50: 2524
  • 24 Mehta G, Srikrishna A, Reddy AV, Nair MS. Tetrahedron 1981; 37: 4543
  • 25 Mehta G, Rao KS. Tetrahedron Lett. 1983; 24: 809
  • 26 Mehta G, Reddy DS, Murty AN. J. Chem. Soc., Chem. Commun. 1983; 824
  • 27 Marchand AP, Chou T.-C. J. Chem. Soc., Perkin Trans. 1 1973; 1948
  • 28 Marchand AP, Allen RW. J. Org. Chem. 1974; 39: 1596
    • 29a Marchand AP, Chou T.-C. Tetrahedron 1975; 31: 2655
  • 30 Marchand AP, Chou T.-C, Barfield M. Tetrahedron Lett. 1975; 3359
  • 31 Marchand AP, Chou T.-C, Ekstrand JD, Van der Helm D. J. Org. Chem. 1976; 41: 1438
  • 32 Marchand AP, Suri SC. Abstracts of Papers, 184th National Meeting of the American Chemical Society, Kansas City, MO, Sept 12, 1982 . American Chemical Society; Washington DC: 1982
    Google Scholar
    • 33a Shen K.-w, Kuebler NA. Tetrahedron Lett. 1973; 2145
    • 33b Chand HR. Synlett 2009; 2545
    • 33c Golobish TD, Dailey WP. J. Org. Chem. 1995; 60: 7865
    • 34a Greenwald R, Chaykovsky M, Corey EJ. J. Org. Chem. 1963; 28: 1128
    • 34b Schollkopf U. In Newer Methods of Preparative Organic Chemistry, Vol. 3. Foerst W. Academic Press; New York: 1964: 111
      Google Scholar
    • 34c Maercker A. Org. React. (Hoboken, NJ, U. S.) 1965; 14: 270
    • 35a McKillop A, Hunt JD, Taylor EC, Kienzle F. Tetrahedron Lett. 1970; 5275
    • 35b McKillop A, Hunt JD, Kienzle F, Bigham E, Taylor EC. J. Am. Chem. Soc. 1973; 95: 3635
  • 36 Byrd JE, Caesar L, Eaton PE, Halpern J. J. Chem. Soc. D 1971; 40
  • 37 Corey EJ, Ravindranathan T. Tetrahedron Lett. 1971; 4753
  • 38 Abley P, Byrd JE, Halpern J. J. Am. Chem. Soc. 1973; 95: 2591
    • 39a Gutsche CD. Org. React. (Hoboken, NJ, U. S.) 1954; 8: 364
    • 39b Gutsche CD, Redmore D. Carbocyclic Ring Expansion Reactions . Academic Press; New York: 1968. Chapter IV
      Google Scholar
  • 40 Jaz J, Davreux JP. Bull. Soc. Chim. Belg. 1965; 74: 370
  • 41 Mock WL, Hartman E. J. Am. Chem. Soc. 1970; 92: 5767
    • 42a Giraitis AP, Bullock JL. J. Am. Chem. Soc. 1937; 59: 951
    • 42b Lumb JT, Whitham GH. Tetrahedron 1965; 21: 499
    • 43a Sauers RR, Tucker RJ. J. Org. Chem. 1963; 28: 876
    • 43b Fachinetti G, Pietra F, Marsili A. Tetrahedron Lett. 1971; 393
  • 44 Smith PA. S, Baer DR. Org. React. (Hoboken, NJ, U. S.) 1960; 11: 157
    • 45a Schollkopf U, Gerhart F. Angew. Chem. Int. Ed. Engl. 1968; 7: 805
    • 45b Gerhart F, Schollkopf U. Tetrahedron Lett. 1968; 6231
  • 46 Gerlach H. Helv. Chim. Acta 1972; 55: 2962
    • 47a Cripps HN, Williams JK, Sharkey WH. J. Am. Chem. Soc. 1958; 80: 751
    • 47b Cripps HN, Williams JK, Sharkey WH. J. Am. Chem. Soc. 1959; 81: 2723
    • 47c Pace V. Homologation Reactions: Reagents Applications and Mechanisms, Vol. 1. Wiley-VCH; Weinheim: 2023
      Google Scholar
    • 47d Pace V. Homologation Reactions: Reagents Applications and Mechanisms, Vol. 2. Wiley-VCH; Weinheim: 2023
      Google Scholar
  • 48 Diels O, Alder K. Justus Liebigs Ann. Chem. 1929; 470: 62
  • 49 Marchand AP, Kaya R. J. Org. Chem. 1983; 48: 5392
  • 50 Marchand AP, Rajapaksa D, Reddy SP, Watson WH, Nagl A. J. Org. Chem. 1989; 54: 5086
  • 51 CCDC 235144 contains the supplementary crystallographic data for compound 37. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures.
  • 52 Diolefination of Cage Diones with the Tebbe Reagent; General Procedure The Tebbe reagent (4 equiv) was added dropwise to a precooled solution of the appropriate cage diol (0.78–1.14 mmol) in dry THF at 0 ℃ under N2, and the mixture was stirred at r.t. for 2 h. When the reaction was complete (TLC), 5% aq NaHCO3 was added and the mixture was extracted with EtOAc. The organic layer was washed with brine (20 mL), dried (Na2SO4), filtered, and concentrated under reduced pressure. The residue was purified by column chromatography (silica gel, 1% EtOAc–PE). 17 Prepared according to the general procedure from cage diol 16 (200 mg, 1.14 mmol) to give a colorless liquid; yield: 148 mg (74%). IR (CH2Cl2): 2980, 2882, 1740, 1668 cm–1. 1H NMR (400 MHz, CDCl3): δ = 1.60 (d, J = 10.9 Hz, 2 H), 2.19 (s, 4 H), 2.26 (d, J = 12.9 Hz, 2 H), 2.37 (s, 2 H), 2.63 (s, 2 H), 4.70 (s, 2 H), 4.84 (s, 2 H). 13C NMR (100.6 MHz, CDCl3): δ = 155.34, 106.17, 54.46, 48.88, 42.11, 33.74, 32.49. HRMS (ESI): m/z [M + H]+ calcd for C13H15: 171.1166; found: 171.1167.