Skip to main content
SpringerLink
Log in

The synthesis and stereospecific solid-state photodecarbonylation of hexasubstituted meso- and d,l-ketones

  • Paper
  • Published:
Photochemical & Photobiological Sciences Aims and scope Submit manuscript

Abstract

Tertiary carbanions were trapped with half an equivalent of diphosgene to give meso- and d,l-hexasubstituted ketones in moderate yields and modest diastereoselectivities. The ketones were also synthesized by a step-wise synthesis in which the carbonyl group was first installed as an acid before activation and the second nucleophilic attack. This second method gave lower yields but similar diastereoselectivites. Steric limits of both methods were also determined. The photolysis of the resulting crystalline ketones gave a mixture of products in solution, but took place chemoselectively and diastereospecifically in the solid-state.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

Notes and references

  1. E. A. Peterson and L. E. Overman, Contiguous stereogenic quaternary carbons: a daunting challenge in natural product synthesis, Proc. Natl. Acad. Sci. U. S. A., 2004, 101, 11943–11948

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  2. B. Dutta, N. Gilboa and I. Marek, Highly diastereoselective preparation of homoallylic alcohols containing two contiguous quaternary stereocenters in acyclic systems from simple terminal alkynes, J. Am. Chem. Soc., 2010, 132, 5588–5589

    Article  CAS  PubMed  Google Scholar 

  3. T. Yoshino, H. Morimoto, G. Lu, S. Matsunaga and M. Shibasaki, Construction of contiguous tetrasubstituted chiral carbon stereocenters via direct catalytic asymmetric aldol reaction of α-isothiocyanato esters with ketones, J. Am. Chem. Soc., 2009, 131, 17082–17083

    Article  CAS  PubMed  Google Scholar 

  4. F. Xue, S. Zhang, L. Liu, W. Duan and W. Wang, Organocatalytic enantioselective cross-aldol reactions of aldehydes with isatines: formation of two contiguous quaternary centered 3-substituted 3-hydroxyindol-2-ones, Chem.-Asian J., 2009, 4, 1664–1667

    Article  CAS  PubMed  Google Scholar 

  5. L. E. Overman and D. A. Watson, Diastereoselection in the formation of contiguous quaternary carbon stereocenters by the intramolecular Heck reaction, J. Org. Chem., 2006, 71, 2600–2667.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  6. Y. Inoue, Asymmetric photochemical reactions in solution, Chem. Rev., 1992, 92, 741–770

    Article  CAS  Google Scholar 

  7. J. Svoboda and B. König, Templated photochemistry: toward catalysts enhancing the efficiency and selectivity of photoreactions in homogeneous solutions, Chem. Rev., 2006, 106, 5413–5430

    Article  CAS  PubMed  Google Scholar 

  8. R. G. Weiss, V. Ramamurthy and G. S. Hammond, Photochemistry in organized and confining media: a model, Acc. Chem. Res., 1993, 26, 530–536

    Article  CAS  Google Scholar 

  9. R. S. H. Liu and G. S. Hammond, Reflection on medium effects on photochemical reactivity, Acc. Chem. Res., 2005, 38, 396–403

    Article  CAS  PubMed  Google Scholar 

  10. L. M. Campos and M. A. Garcia-Garibay, Reactive intermediates in crystals: form and function, in Reactive Intermediates, ed. M. S. Platz, M. Jones and R. Moss, Hoboken, NJ, 2007, ch. 7, pp. 271–331.

    Google Scholar 

  11. M. Nishijima, T. C. S. Pace, A. Nakamura, T. Mori, T. Wada, C. Bohne and Y. Inoue, Supramolecular photochirogenesis with biomolecules. Mechanistic studies on the enantiodifferentiation for the photocyclodimerization of 2-anthracenecarboxylate mediated by bovine serum albumin, J. Org. Chem., 2007, 72, 2707–2715

    Article  CAS  PubMed  Google Scholar 

  12. C. L. D. Gibb, A. K. Sundaresan, V. Ramamurthy and B. C. Gibb, Templation of the excited-state chemistry of α-(n-alkyl) dibenzyl ketones: how guest packing within a nanoscale suptramolecular capsule influences photochemistry, J. Am. Chem. Soc., 2008, 130, 4069–4080

    Article  CAS  PubMed  Google Scholar 

  13. P. Montes-Navajas and H. Garcia, Cucurbituril complexation enhances intersystem crossing and triplet lifetime of2, 4, 6-triphenylpyrylium ion, J. Phys. Chem. C, 2010, 114, 2034–2038.

    Article  CAS  Google Scholar 

  14. N. J. Turro, From boiling stones to smart crystals: supramolecular and magnetic isotope control of radical-radical reactions in zeolites, Acc. Chem. Res., 2000, 33, 637–646

    Article  CAS  PubMed  Google Scholar 

  15. J. C. Scaiano and H. Garcia, Intrazeolite photochemistry: toward supramolecular control of molecular photochemistry, Acc. Chem. Res., 1999, 32, 783–793

    Article  CAS  Google Scholar 

  16. V. Ramamurthy and M. A. Garcia-Garibay, Zeolites as supramolecular hosts for photochemical transformations, in Supramolecular Chemistry, ed. G. Alberti and T. Bein, Elsevier, New York, 1996, vol. 7, ch. 24, pp. 693–719.

    Google Scholar 

  17. J. Xu and R. G. Weiss, Enantioselectivity of prochiral radical-pair recombinationsReaction cavity differentiation in polyethylene films, Org. Lett., 2003, 5, 3077–3080

    Article  CAS  PubMed  Google Scholar 

  18. T. Mori, Y. Inoue and R. G. Weiss, Enhanced photodecarboxylation of an aryl ester in polyethylene films, Org. Lett., 2003, 5, 4661–4664.

    Article  CAS  PubMed  Google Scholar 

  19. V. Ramamurthy and K. Venkatesan, Photochemical reactions of organic crystals, Chem. Rev., 1987, 87, 433–481

    Article  CAS  Google Scholar 

  20. J. N. Gamlin, R. Jones, M. Leibovitch, B. Patrick, J. R. Scheffer and J. Trotter, The ionic auxiliary concept in solid state organic photochemistry, Acc. Chem. Res., 1996, 29, 203–209

    Article  CAS  Google Scholar 

  21. M. A. Garcia-Garibay, Engineeringcarbene rearrangements in crystals: from molecular information to solid-state reactivity, Acc. Chem. Res., 2003, 36, 491–498

    Article  CAS  PubMed  Google Scholar 

  22. J. R. Scheffer, Crystal lattice control of unimolecular photorearrangements, Acc. Chem. Res., 1980, 13, 283–290

    Article  CAS  Google Scholar 

  23. L. R. MacGillivray, G. S. Papaefstathiou, T. Friscic, T. D. Hamilton, D. K. Bucar, Q. Chu, D. B. Varshney and I. G. Georgiev, Supramolecular control of reactivity in the solid state: from templates to ladderanes to metal-organic frameworks, Acc. Chem. Res., 2008, 41, 280–291.

    Article  CAS  PubMed  Google Scholar 

  24. S. Shiraki and M. A. Garcia-Garibay, Carbon-carbon bond formation by the photoelimination of small molecules in solution and in crystals, in Handbook of Synthetic Photochemistry, ed. A. Albini and M. Fagnini, Wiley-VCH, Weinheim, 2010, ch. 2, pp. 25–66

    Google Scholar 

  25. C. J. Mortko and M. A. Garcia-Garibay, Stereospecific synthesis of compounds with adjacent chiral quaternary centers in solid-to-solid reactions, in Topics in Stereochemistry, ed. S. E. Denmark and J. S. Siegel, Wiley-Interscience, Hoboken, NJ, 2006, vol. 25, ch. 7, 205–253.

    Chapter  Google Scholar 

  26. M. Veerman, M. J. E. Resendiz and M. A. Garcia-Garibay, Large-scale photochemical reactions of nanocrystalline suspensions: a promising green chemistry method, Org. Lett., 2006, 8, 2615-1617

  27. C. J. Mortko and M. A. Garcia-Garibay, Green chemistry strategies using crystal-to-crystal photoreactions: stereoselective synthesis and decarbonylation of trans-α, αα-dialkenoylcyclohexanones, J. Am. Chem. Soc., 2005, 127, 7994–7995.

    Article  CAS  PubMed  Google Scholar 

  28. M. A. Garcia-Garibay and L. Campos, Photochemical decarbonylation of ketones: recent advances and reactions in crystalline solids, in The Handbook of Organic Photochemistry and Photobiology, ed. W. Horspool, CRC Press, Boca Raton, FL, 2003, ch. 48.

    Google Scholar 

  29. M. A. Garcia-Garibay, The entropic enlightenment of organic photochemistry: strategic modifications of intrinsic decay pathways using an information-based approach, Photochem. Photobiol. Sci., 2010, 9, 1574–1588.

    Article  CAS  PubMed  Google Scholar 

  30. T. Choi, K. Peterfy, S. I. Khan and M. A. Garcia-Garibay, Molecular control of solid-state reactivity and biradical formation from crystalline ketones, J. Am. Chem. Soc., 1996, 118, 12477–12478

    Article  CAS  Google Scholar 

  31. T. Choi, D. Cizmeciyan, S. I. Kahn and M. A. Garcia-Garibay, An efficient solid-to-solid reaction via a steady-state phase separation mechanism, J. Am. Chem. Soc., 1995, 117, 12893–12894

    Article  CAS  Google Scholar 

  32. K. Peterfy and M. A. Garcia-Garibay, Generation and reactivity of a triplet 1,4-biradical confomationally trapped in a crystalline cyclopentanone, J. Am. Chem. Soc., 1998, 120, 4540–4541.

    Article  CAS  Google Scholar 

  33. M. J. E. Resendiz and M. A. Garcia-Garibay, Hammett analysis of photodecarbonylation in crystalline 1, 3-diarylacetones, Org. Lett., 2005, 7, 371–374

    Article  CAS  PubMed  Google Scholar 

  34. T. Choe, S. I. Khan and M. A. Garcia-Garibay, Combination vs. disproportionation in dialkyl biradicals. Selectivity reversal in a crystalline solid, Photochem. Photobiol. Sci., 2006, 5, 449451

    Article  CAS  Google Scholar 

  35. F. Family and M. A. Garcia-Garibay, Photodecarbonylation of ketodiacids as ammonium salts: efficient formation of C-C bonds between adjacent quaternary centers in the crystalline state, J. Org. Chem., 2009, 74, 2476–2480.

    Article  CAS  PubMed  Google Scholar 

  36. D. Ng, Z. Yang and M. A. Garcia-Garibay, Total synthesis of (±)- herbertenolide by stereospecific formation of vicinal quaternary centers in a crystalline ketone, Org. Lett., 2004, 6, 645–647.

    Article  CAS  PubMed  Google Scholar 

  37. A. Natarajan, D. Ng, Z. Yang and M. A. Garcia-Garibay, Parallel syntheses of (+)- and (-)-a-cuparenone by radical combination in crystalline solids, Angew. Chem., Int. Ed., 2007, 46, 64856487.

    Article  Google Scholar 

  38. M. J. E. Resendiz, A. Natarajan and M. A. Garcia-Garibay, Diastereoselective synthesis and spin-dependent photodecarbonylation of di(3-phenyl-2-pyrrolidinon-3-yl)ketones: synthesis of nonadjacent and adjacent stereogenic quaternary centers, Chem. Commun., 2008, 193–195

    Google Scholar 

  39. M. J. E. Resendiz, F. Family, K. Fuller, L. M. Campos, S. I. Khan, N. V. Lebedeva, M. D. E. Forbes and M. A. Garcia-Garibay, Radical reactions with double memory of chirality (2MOC) for the enantiospecific synthesis of adjacent stereogenic quaternary centers in solution: cleavage and bonding faster than radical rotation, J. Am. Chem. Soc., 2009, 131, 8425–8433.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  40. E. Vedejs, A. W. Kruger, N. Lee, S. T. Sakata, M. Stec and E. Suna, Enantioselective enolate protonation with chiral anilines: scope, structural requirements, and mechanistic implications, J. Am. Chem. Soc., 2000, 122, 4602–4607.

    Article  CAS  Google Scholar 

  41. D. Weiss, The Norrish type-I reaction in cycloalkanone photochemistry, in Organic Photochemistry, ed. A. Padwa, Marcel Deker, New York, 1981, vol. 5, pp. 347–420

    Google Scholar 

  42. C. Bohne, Norrish type I processes of ketones: selected examples and synthetic applications, in CRC Handbook of Organic Photochemistry and Photobiology, ed. W. M. Horspool and P. S. Song, CRC Press, Boca Raton, FL, 1995, pp. 423–429.

    Google Scholar 

  43. N. V. Lebedeva, V. F. Tarasov, M. J. E. Resendiz, M. A. Garcia-Garibay, R. C. White and M. D. E. Forbes, The missing link between molecular triplets and spin-polarized free radicals: room temperature triplet states of nanocrystallline radical pairs, J. Am. Chem. Soc., 2010, 132, 8284.

    Article  CAS  Google Scholar 

  44. L. I. Peterson, Meso-dl isomerization of 2, 3-dimethyl-2, 3-diphenylsuccinonitrile, J. Am. Chem. Soc., 1967, 89, 2677–2681.

    Article  CAS  Google Scholar 

  45. R. L. Huang and L. Kum-Tatt, Synthetic estrogens. Part II. The synthesis of tetra-alkyldibenzyls and substituted succinonitriles by freeradical dimerisation, J. Chem. Soc., 1954, 2570–2577.

    Google Scholar 

  46. Y. L. Lam, L. L. Koh and H. H. Huang, Crystal structures of meso- and (±)-2, 3-dicyano-2-3-diphenylbutane and 3, 4-dicyano-3, 4-diphenylhexane, J. Chem. Res., Synop., 1991, 212–213.

    Google Scholar 

  47. C. de Luca, A. Inesi and L. Rampazzo, Electroreduction of methyl 2-bromo-2-phenylpropanoate on a vitreous carbon electrode: meso- and DL-dimethyl2, 3-dimethyl-2, 3-diphenylsuccinate, J. Chem. Soc., Perkin Trans. 2, 1982, 1403–1407.

    Google Scholar 

  48. K. Biswas and S. Woodward, Stereoselective 1, 4-addition of Grignard reagents to a, β-enamdes using a combined chiral auxillarycatalyst approach, Tetrahedron: Asymmetry, 2008, 19, 1702–1708

    Article  CAS  Google Scholar 

  49. K. Ogura, S. Mitamura, K. Kishi and G. Tsuchihashi, A new synthesis of 2-arylpropanoates using methyl methylthiomethyl sulfoxide, Synthesis, 1979, 880–882.

    Google Scholar 

  50. H. Brunner and P. Schmidt, Naproxen derivatives by enantioselective decarboxylation, Eur. J. Org. Chem., 2000, 2119–2133

    Google Scholar 

  51. M. E. Ellison, D. Ng, H. Dang and M. A. Garcia-Garibay, Enantiospecific synthesis of vicinal stereogenic tertiary and quaternary centers by combination of configurationally-trapped radical pairs in crystalline solids, Org. Lett., 2003, 5, 2531–2534.

    Article  CAS  PubMed  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Chemistry and Biochemistry, University of California, Los Angeles, CA, 90095-1569, USA

    Saori Shiraki, Arunkumar Natarajan & Miguel A. Garcia-Garibay

Authors
  1. Saori Shiraki
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Arunkumar Natarajan
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Miguel A. Garcia-Garibay
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Miguel A. Garcia-Garibay.

Additional information

This article is published as part of a themed issue in honour of Yoshihisa Inoue’s research accomplishments on the occasion of his 60th birthday.

CCDC reference numbers 814323 & 814324. For crystallographic data in CIF or other electronic format see DOI: 10.1039/c1pp05080j

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Shiraki, S., Natarajan, A. & Garcia-Garibay, M.A. The synthesis and stereospecific solid-state photodecarbonylation of hexasubstituted meso- and d,l-ketones. Photochem Photobiol Sci 10, 1480–1487 (2011). https://doi.org/10.1039/c1pp05080j

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1039/c1pp05080j

Search

Navigation