C–H Activation via Radical Processes Using Photo-Excited Ketones

Chapter
Part of the Topics in Heterocyclic Chemistry book series (TOPICS, volume 54)

Abstract

This chapter covered recent advancements in nonreactive C(sp3)–H bond functionalization using photo-excited aryl ketones. The C–H bond cleaving ability of photo-excited ketones plays an important role in these reactions. Transformations targeting nonreactive C–H bonds can dramatically simplify synthetic sequences and improve synthetic efficiency as described in this chapter.

Keywords

C(sp3)–H bond functionalization Free radicals Heterocycles Insertion Photoreaction Substitution 

References

  1. 1.
    Dyker G (ed) (2005) Handbook of C–H transformations, vol 1, 2. Wiley-VCH, WeinheimGoogle Scholar
  2. 2.
    Paquette LA, Fuchs PL (eds) (2007) Handbook of reagents for organic synthesis: reagents for direct functionalization of C–H bonds. Wiley, ChichesterGoogle Scholar
  3. 3.
    Davies HML, Du Bois J, Yu JQ (eds) (2011) C–H functionalization in organic synthesis (Special Issue). Chem Soc Rev 40(4):1845–2040Google Scholar
  4. 4.
    Ciamician G, Silber P (1900) Ber Dtsch Chem Ges 33:2911–2913CrossRefGoogle Scholar
  5. 5.
    Bachmann WE (1934) Benzopinacol. Org Synth 2:71–72Google Scholar
  6. 6.
    Yang NC, Yang DDH (1958) Photochemical reactions of ketones in solution. J Am Chem Soc 80:2913–2914CrossRefGoogle Scholar
  7. 7.
    Breslow R (2001) Biomimetic selectivity. Chem Rec 1:3–11CrossRefGoogle Scholar
  8. 8.
    Preston GW, Wilson AJ (2013) Photo-induced covalent cross-linking for the analysis of biomolecular interactions. Chem Soc Rev 42:3289–3301CrossRefGoogle Scholar
  9. 9.
    Herrera AJ, Rondón M, Suárez E (2007) Stereocontrolled photocyclization of 1,2-diketones applied to carbohydrate models: a new entry to C-ketosides. Synlett:1851–1856Google Scholar
  10. 10.
    Herrera AJ, Rondón M, Suárez E (2008) Stereocontrolled photocyclization of 1,2-diketones: application of a 1,3-acetyl group transfer methodology to carbohydrates. J Org Chem 73:3384–3391CrossRefGoogle Scholar
  11. 11.
    Kawamata T, Nagatomo M, Inoue M (2017) Total synthesis of zaragozic acid C: implementation of photochemical C(sp3)–H acylation. J Am Chem Soc 139:1814–1817CrossRefGoogle Scholar
  12. 12.
    Kamijo S, Hoshikawa T, Inoue M (2010) Regio- and stereoselective acylation of saturated carbocycles via Norrish–Yang photocyclization. Tetrahedron Lett 51:872–874CrossRefGoogle Scholar
  13. 13.
    Kamijo S, Hoshikawa T, Inoue M (2011) Photochemically induced radical transformation of C(sp3)–H bonds to C(sp3)–CN bonds. Org Lett 13:5928–5931CrossRefGoogle Scholar
  14. 14.
    Hoshikawa T, Yoshioka S, Kamijo S, Inoue M (2013) Photoinduced direct cyanation of C(sp3)–H bonds. Synthesis 45:874–887CrossRefGoogle Scholar
  15. 15.
    Gong J, Fuchs PL (1996) Alkynylation of C−H bonds via reaction with acetylenic triflones. J Am Chem Soc 118:4486–4487CrossRefGoogle Scholar
  16. 16.
    Xiang JS, Fuchs PL (1996) Mechanistic aspects of the C–H alkynylation reaction of acetylenic triflones. Determination of phenyl versus cyclohexyl migratory aptitude for a vinylidine carbene. Tetrahedron Lett 37:5269–5272CrossRefGoogle Scholar
  17. 17.
    Xiang J, Jiang W, Fuchs PL (1997) Scope and limitations of functionalized acetylenic triflones in the direct alkynylation of C-H bonds. Tetrahedron Lett 38:6635–6638CrossRefGoogle Scholar
  18. 18.
    Kamijo S, Hoshikawa T, Inoue M (2013) Photochemically induced radical alkynylation of C(sp3)–H bonds. Org Biomol Chem 11:164–169CrossRefGoogle Scholar
  19. 19.
    Nagatomo M, Yoshioka S, Inoue M (2015) Enantioselective radical alkynylation of C(sp3)-H bonds using sulfoximine as a traceless chiral auxiliary. Chem Asian J 10:120–123CrossRefGoogle Scholar
  20. 20.
    Yoshioka S, Nagatomo M, Inoue M (2015) Application of two direct C(sp3)–H functionalizations for total synthesis of (+)-lactacystin. Org Lett 17:90–93CrossRefGoogle Scholar
  21. 21.
    Xiang J, Fuchs PL (1996) Alkenylation of C−H bonds via reaction with vinyl and dienyl triflones. Stereospecific synthesis of trisubstituted vinyl triflones via organocopper addition to acetylenic triflones. J Am Chem Soc 118:11986–11987CrossRefGoogle Scholar
  22. 22.
    Xiang J, Jiang W, Gong J, Fuchs PL (1997) Stereospecific alkenylation of C−H bonds via reaction with β-heteroatom-functionalized trisubstituted vinyl triflones. J Am Chem Soc 119:4123–4129CrossRefGoogle Scholar
  23. 23.
    Amaoka Y, Nagatomo M, Watanabe M, Tao K, Kamijo S, Inoue M (2014) Photochemically induced radical alkenylation of C(sp3)–H bonds. Chem Sci 5:4339–4345CrossRefGoogle Scholar
  24. 24.
    Paul S, Guin J (2017) Radical C(sp3)–H alkenylation, alkynylation and allylation of ethers and amides enabled by photocatalysis. Green Chem 19:2530–2534CrossRefGoogle Scholar
  25. 25.
    Kamijo S, Kamijo K, Maruoka K, Murafuji T (2016) Aryl ketone catalyzed radical allylation of C(sp3)–H bonds under photoirradiation. Org Lett 18:6516–6519CrossRefGoogle Scholar
  26. 26.
    Kamijo S, Takao G, Kamijo K, Hirota M, Tao K, Murafuji T (2016) Photo-induced substitutive introduction of the aldoxime functional group to carbon chains: a formal formylation of non-acidic C(sp3)–H bonds. Angew Chem Int Ed 55:9695–9699CrossRefGoogle Scholar
  27. 27.
    Hoshikawa T, Inoue M (2013) Photoinduced direct 4-pyridination of C(sp3)–H bonds. Chem Sci 4:3118–3123CrossRefGoogle Scholar
  28. 28.
    Kamijo S, Kamijo K, Murafuji T (2017) Synthesis of alkylated pyrimidines via photoinduced coupling using benzophenone as a mediator. J Org Chem 82:2664–2671CrossRefGoogle Scholar
  29. 29.
    Lipp A, Lahm G, Opatz T (2016) Light induced C–C coupling of 2-chlorobenzazoles with carbamates, alcohols, and ethers. J Org Chem 81:4890–4897CrossRefGoogle Scholar
  30. 30.
    Kamijo S, Hirota M, Tao K, Watanabe M, Murafuji T (2016) Photoinduced sulfonylation of cyclic ethers. Tetrahedron Lett 55:5551–5554CrossRefGoogle Scholar
  31. 31.
    Kamijo S, Watanabe M, Kamijo K, Tao K, Murafuji T (2016) Synthesis of aliphatic azides by photoinduced C(sp3)–H azidation. Synlett 48:115–121Google Scholar
  32. 32.
    Kamijo S, Tao K, Takao G, Murooka H, Murafuji T (2015) Ether derivatization via two-step protocol comprised of photochemical ethereal C–H bond chlorination and nucleophilic substitution. Tetrahedron Lett 56:1904–1907CrossRefGoogle Scholar
  33. 33.
    Han L, Xia J-B, You L, Chen C (2017) Ketone-catalyzed photochemical C(sp3)–H chlorination. Tetrahedron 73:3696–3701CrossRefGoogle Scholar
  34. 34.
    Xia J-B, Zhu C, Chen C (2013) Visible light-promoted metal-free C–H activation: diarylketone-catalyzed selective benzylic mono- and difluorination. J Am Chem Soc 135:17494–17500CrossRefGoogle Scholar
  35. 35.
    Cantillo D, de Frutos O, Rincón JA, Mateos C, Kappe CO (2014) A continuous-flow protocol for light-induced benzylic fluorinations. J Org Chem 79:8486–8490CrossRefGoogle Scholar
  36. 36.
    Bume DD, Pitts CR, Jokhai RT, Lectka T (2016) Direct, visible light-sensitized benzylic C–H fluorination of peptides using dibenzosuberenone: selectivity for phenylalanine-like residues. Tetrahedron 77:6031–6036CrossRefGoogle Scholar
  37. 37.
    Kee CW, Chin KF, Wong MW, Tan C-H (2014) Selective fluorination of alkyl C–H bonds via photocatalysis. Chem Commun 50:8211–8214CrossRefGoogle Scholar
  38. 38.
    Xia J-B, Zhu C, Chen C (2014) Visible light-promoted metal-free sp3-C–H fluorination. Chem Commun 50:11701–11704CrossRefGoogle Scholar
  39. 39.
    Kamon T, Irifune Y, Tanaka T, Yoshimitsu T (2011) Total synthesis of (±)-kainic acid: a photochemical C–H carbamoylation approach. Org Lett 13:2674–2677CrossRefGoogle Scholar
  40. 40.
    Kamijo S, Hoshikawa T, Inoue M (2011) Photoinduced carbamoylation of ethereal C–H bonds using pentafluorophenyl isocyanate. Tetrahedron Lett 52:2885–2888CrossRefGoogle Scholar
  41. 41.
    Giese B (1983) Formation of CC bonds by addition of free radicals to alkenes. Angew Chem Int Ed Engl 22:753–764CrossRefGoogle Scholar
  42. 42.
    Srikanth GSC, Castle SL (2005) Advances in radical conjugate additions. Tetrahedron 61:10377–10441CrossRefGoogle Scholar
  43. 43.
    Elad D, Youssefyef RD (1964) The photoaddition of cyclic ethers to 1-octene. J Org Chem 29:2031–2032CrossRefGoogle Scholar
  44. 44.
    Rosenthal I, Elad D (1967) The photoalkylation of cyclic ethers. Tetrahedron 23:3193–3204CrossRefGoogle Scholar
  45. 45.
    Fraser-Reid B, Anderson BC, Hicks DR, Walker DL (1977) Synthetic applications of the photochemically induced addition of oxycarbinyl species to α-enones. Part II. The addition of ketals, aldehydes, and polyfunctional species. Can J Chem 55:3986–3995CrossRefGoogle Scholar
  46. 46.
    Sakakibara T, Takaide A, Seta A (1992) Photoaddition reactions of 3-nitro-2-enopyranoside derivatives in 1,3-dioxolane. Carbohydr Res 226:271–278CrossRefGoogle Scholar
  47. 47.
    Inomata K, Suhara H, Kinoshita H, Kotake H (1988) Photoinduced masked-formylation of vinylsulfone derivatives with 1,3-dioxolane. Application to the synthesis of 3,4-disubstituted pyrroles. Chem Lett 17:813–816CrossRefGoogle Scholar
  48. 48.
    Ogura K, Yanagisawa A, Fujino T, Takahashi K (1988) An efficient acceptor of 1-hydroxy(or alkoxy)alkyl radicals – ketene dithioacetal S,S-dioxide. Tetrahedron Lett 29:5387–5390CrossRefGoogle Scholar
  49. 49.
    Ogura K, Kayano A, Akazome M (1997) High 1,2-asymmetric induction in radical reactions: radical addition to γ-hydroxy α,β-unsaturated carboxylic esters and sulfones. Bull Chem Soc Jpn 70:3091–3101CrossRefGoogle Scholar
  50. 50.
    Mase N, Watanabe Y, Toru T (1998) Photo-induced intermolecular radical β-addition to chiral α-(Arylsulfinyl) enones. Bull Chem Soc Jpn 71:2957–2965CrossRefGoogle Scholar
  51. 51.
    Yavorskyy A, Shvydkiv O, Hoffmann N, Nolan K, Ogelgemöller M (2012) Parallel microflow photochemistry: process optimization, scale-up, and library synthesis. Org Lett 14:4342–4345CrossRefGoogle Scholar
  52. 52.
    Santiago E, de Alvarenga S, Mann J (1993) Photocatalysed addition of pyrrolidines to butenolides: a concise synthesis of the pyrrolizidine alkaloid ring system. J Chem Soc Perkin Trans 1:2141–2142Google Scholar
  53. 53.
    Bertrand S, Glapski C, Hoffmann N, Pete J-P (1999) Highly efficient photochemical addition of tertiary amines to electron deficient alkenes. Diastereoselective addition to (5R)-5-menthyloxy-2[5H]-furanone. Tetrahedron Lett 40:3169–3172CrossRefGoogle Scholar
  54. 54.
    Kamijo S, Takao G, Kamijo K, Tsuno T, Ishiguro K, Murafuji T (2016) Alkylation of nonacidic C(sp3)–H bonds by photoinduced catalytic Michael-type radical addition. Org Lett 18:4912–4915CrossRefGoogle Scholar

Copyright information

© Springer International Publishing AG, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Graduate School of Sciences and Technology for InnovationYamaguchi UniversityYamaguchiJapan

Personalised recommendations