Synlett 2002(5): 0674-0686
DOI: 10.1055/s-2002-25328
ACCOUNT
© Georg Thieme Verlag Stuttgart · New York

Synthetic Radical Reactions in Aqueous Media

Hideki Yorimitsu, Hiroshi Shinokubo, Koichiro Oshima*
Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Yoshida, Sakyo-ku, Kyoto 606-8501, Japan
Fax: +81(75)7534863; e-Mail: oshima@fm1.kuic.kyoto-u.ac.jp;
Further Information

Publication History

Received 30 August 2001
Publication Date:
07 February 2007 (online)

Abstract

This account focuses on the discovery and the rationalization of solvent effects, especially those of water, on synthetically useful radical reactions. Noteworthy advantages were observed during the course of our study on radical reactions in aqueous media. The established advantages of water as a solvent for radical reactions are (1) facile room-temperature atom transfer radical cyclization of allyl iodoacetate, (2) highly efficient construction of medium and large rings via radical cyclization of ω-alkenyl iodoacetate, (3) enhancement of intermolecular radical addition, and (4) the highest deuterium incorporation in the deuterative reduction of organic halides. The favorable solvent effects of water are mainly due to its extremely high polarity, strong hydrogen bonding ability, and lack of easily transferable hydrogen via a radical process.

  • 1 Introduction

  • 2 Triethylborane-Induced Iodine Atom Transfer Radical Cyclization of Iodo Acetals and Allylic Iodoacetates in Aqueous Media

  • 3 Iodine Atom Transfer Radical Cyclization of N-Allyl-2-Iodo Amides in Water

  • 4 Atom Transfer Radical Addition of Halogenated Compounds in Water

  • 5 Radical Addition of Iodoacetamide to Alkenes with a Water-Soluble Radical Initiator in an Aqueous Medium: Facile Synthesis of γ-Lactones

  • 6 Triethylborane-Induced Bromine Atom Transfer Radical Addition in Aqueous Media: Study of the Solvent Effect on Radical Addition Reaction

  • 7 Reduction of Organic Halides with Tri-2-Furylgermane in Water

  • 8 Radical Reaction by a Combination of Phosphinic Acid and a Base in Aqueous Media: Reduction and Deuteration of Organic Halides

  • 9 Triethylborane-induced Radical Allylation of α-Halo Carbonyl Compounds with Allylgallium Reagents in Aqueous Media

  • 10 Outlook

    References

  • 1a Radicals in Organic Synthesis   Renaud P. Sibi MP. Wiley-VCH; Weinheim: 2001. 
  • 1b Curran DP. Porter NA. Giese B. Stereochemistry of Radical Reactions   VCH Verlagsgesellschaft GmbH.; Weinheim: 1996. 
  • 1c Giese B. Kopping B. Göbel T. Dickhaut J. Thoma G. Kulicke KJ. Trach F. Org. React.  1996,  48:  301 
  • 1d Curran DP. In Comprehensive Organic Synthesis   Vol. 4:  Trost BM. Fleming I. Pergamon Press; Oxford: 1991.  Chap. 4.1.
  • 1e Curran DP. In Comprehensive Organic Synthesis   Vol. 4:  Trost BM. Fleming I. Pergamon Press; Oxford: 1991.  Chap. 4.2.
  • 2a Bagulay PA. Walton JC. Angew. Chem., Int. Ed.  1998,  37:  3072 
  • 2b Chatgilialoglu C. Radicals in Organic Synthesis   Vol. 1:  Renaud P. Sibi MP. Wiley-VCH; Weinheim: 2001.  Chap.1.3.
  • 3 Giese B. Kopping B. Chatgilialoglu C. Tetrahedron Lett.  1989,  30:  681 
  • 4a Nozaki K. Oshima K. Utimoto K. J. Am. Chem. Soc.  1987,  109:  2547 
  • 4b Oshima K. Utimoto K. J. Syn. Org. Chem. Jpn.  1989,  47:  40 
  • 4c Yorimitsu H. Oshima K. Radicals in Organic Synthesis   Vol. 1:  Renaud P. Sibi MP. Wiley-VCH; Weinheim: 2001.  Chap. 1.2.
  • 4d Kita Y. Matsugi M. See also: Radicals in Organic Synthesis   Vol. 1:  Renaud P. Sibi MP. Wiley-VCH; Weinheim: 2001.  Chap. 1.1.
  • For review:
  • 5a Renaud P. Gerster M. Angew. Chem. Int. Ed.  1998,  37:  2562 
  • 5b Radicals in Organic Synthesis   Vol.1:  Renaud P. Sibi MP. Wiley-VCH; Weinheim: 2001.  Chap. 4.
  • 5c Murakata M. Hoshino O. J. Synth. Org. Chem. Jpn.  2001,  59:  560 
  • 6a Curran DP. Porter NA. Giese B. Stereochemistry of Radical Reactions   VCH Verlagsgesellschaft GmbH; Weinheim: 1996.  p.4 
  • 6b Curran DP. In Comprehensive Organic Synthesis   Vol. 4:  Trost BM. Fleming I. Pergamon Press; Oxford: 1991.  Chap. 4.1. p.720 
  • 7a Avila DV. Ingold KU. Lusztyk J. Green WH. Procopio DR. J. Am. Chem. Soc.  1995,  117:  2929 
  • 7b Tronche C. Martinez FN. Horner JH. Newcomb M. Senn M. Giese B. Tetrahedron Lett.  1996,  37:  5845 
  • 7c Luedtke A. Meng K. Timberlake JW. Tetrahedron Lett.  1987,  28:  4255 
  • 7d Kanabuskaminska JM. Gilbert BC. Griller D. J. Am. Chem. Soc.  1989,  111:  3311 
  • 7e Renaud P. Ribezzo M. J. Am. Chem. Soc.  1991,  113:  7803 
  • 7f Beckwith ALJ. Cliff MD. Schiesser CH. Tetrahedron  1992,  48:  4641 
  • 7g Beckwith ALJ. Bowey VW. Ingold KU. J. Am. Chem. Soc.  1992,  114:  4983 
  • 7h Avila DV. Brown CE. Ingold KU. Lusztyk J. J. Am. Chem. Soc.  1993,  115:  466 
  • 7i Tanko JM. Suleman NK. Hulvey GA. Park A. Powers JE. J. Am. Chem. Soc.  1993,  115:  4520 
  • 7j Tanko JM. Suleman NK. J. Am. Chem. Soc.  1994,  116:  5162 
  • 7k Cozens FL. O" Neill M. Bogdanova R. Schepp N. J. Am. Chem. Soc.  1997,  119:  10652 
  • 7l Horner JH. Tanaka N. Newcomb M. J. Am. Chem. Soc.  1998,  120:  10379 
  • 7m Newcomb M. Horner JH. Whitted PO. Crich D. Huang XH. Yao QW. Zipse H. J. Am. Chem. Soc.  1999,  121:  10685 
  • 8 Rideout DC. Breslow R. J. Am. Chem. Soc.  1980,  102:  7816 
  • 9a Li C.-J. Chan T.-H. Organic Reactions in Aqueous Media   John Wiley & Sons Inc.; New York: 1997. 
  • 9b Grieco PA. Organic Synthesis in Water   Blackie Academic & Professional; London: 1998. 
  • 9c Lubineau A. Auge J. In Modern Solvents in Organic Synthesis   Knochel P. Springer-Verlag; Berlin, Heidelberg: 1999. 
  • 10a Protonated N-chloroamine: Minisci F. Synthesis  1973,  1 
  • 10b Group 14 metal hydride: Yamazaki O. Togo H. Nogami G. Yokoyama M. Bull. Chem. Soc. Jpn.  1997,  70:  2519 
  • 10c See also: Breslow R. Light J. Tetrahedron Lett.  1990,  31:  2957 
  • 10d See also: Rai R. Collum DB. Tetrahedron Lett.  1994,  35:  6221 
  • 10e See also: Maitra U. Sarma KD. Tetrahedron Lett.  1994,  35:  7861 
  • 10f Radical addition to imine: Miyabe H. Ueda M. Naito T. J. Org. Chem.  2000,  65:  5043 
  • 10g See also: Miyabe H. Ueda M. Naito T. Chem. Commun.  2000,  2059 
  • 10h Radical-polar crossover reaction: Patro B. Merrett MC. Makin SD. Murphy JA. Parkes KEB. Tetrahedron Lett.  2000,  41:  421 
  • 10i See also: Bashir N. Murphy JA. Chem. Commun.  2000,  627 
  • 10j Zinc-mediated reaction: Petrier C. Dupuy C. Luche JL. Tetrahedron Lett.  1986,  27:  3149 
  • 10k See also: Giese B. Damm W. Roth M. Zehnder M. Synlett  1992,  441 
  • 10l Reformatski reaction: Bieber LW. Malvestiti I. Storch EC. J. Org. Chem.  1997,  62:  9061 
  • 10m Other redox-induced radical reaction: Dalko PI. Tetrahedron  1995,  51:  7579 
  • 10n Bromination: Shaw H. Perlmutter HD. Gu Chen Arco SD. Quibuyen TO. J. Org. Chem.  1997,  62:  236 
  • 10o Miscellaneous reactions: Sibi MP. Ji J. Sausker JB. Jasperse CP. J. Am. Chem. Soc.  1999,  121:  7517 
  • 10p See also: Bietti M. Baciocchi E. Engberts JBFN. Chem. Soc., Chem. Commun.  1996,  1307 
  • 10q See also: Testaferri L. Tiecco M. Tingoli M.
    J. Chem. Soc., Chem. Commun.  1978,  93 
  • 10r See also: Flyunt R. Bazzanini R. Chatgilialoglu C. Mulazzani QG. J. Am. Chem. Soc.  2000,  122:  4225 ; see also Refs.7a,b
  • 11a Yorimitsu H. Nakamura T. Shinokubo H. Oshima K. J. Org. Chem.  1998,  63:  8604 
  • 11b Yorimitsu H. Nakamura T. Shinokubo H. Oshima K. Omoto K. Fujimoto H. J. Am. Chem. Soc.  2000,  122:  11041 
  • 12a Curran DP. Synthesis  1988,  417 
  • 12b Curran DP. Synthesis  1988,  489 
  • 12c Curran DP. Chen M.-H. Kim D. J. Am. Chem. Soc.  1986,  108:  2489 
  • 13a Stork G. Sher PM. Chen H.-L. J. Am. Chem. Soc.  1986,  108:  6384 
  • 13b Stork G. Mook RJR. Biller SA. Rychnovsky SD. J. Am. Chem. Soc.  1983,  105:  3741 
  • 13c Ueno Y. Moriya O. Chino K. Watanabe M. Okawara M. J. Chem. Soc., Perkin Trans. 1  1986,  108:  1351 
  • 13d Ueno Y. Chino K. Watanabe M. Moriya O. Okawara M. J. Am. Chem. Soc.  1982,  104:  5564 
  • 14 Srikrishna A. Radicals in Organic Synthesis   Vol. 2:  Renaud P. Sibi MP. Wiley-VCH; Weinheim: 2001.  Chap. 3.1.4.
  • 15 Barone V. Cossi M. J. Phys. Chem. A.  1998,  102:  1995 
  • 16 Wakabayashi K. Yorimitsu H. Shinokubo H. Oshima K. Bull. Chem. Soc. Jpn.  2000,  73:  2377 
  • 17 Nakamura T. Yorimitsu H. Shinokubo H. Oshima K. Synlett  1998,  1351 
  • 18a Yorimitsu H. Wakabayashi K. Shinokubo H. Oshima K. Tetrahedron Lett.  1999,  40:  519 
  • 18b Yorimitsu H. Wakabayashi K. Shinokubo H. Oshima K. Bull. Chem. Soc. Jpn.  2001,  74:  1963 
  • 19 Yorimitsu H. Shinokubo H. Matsubara S. Oshima K. Omoto K. Fujimoto H. J. Org. Chem.  2001,  66:  7776 
  • 20 Kharasch MS. Skell PS. Fisher P. J. Am. Chem. Soc.  1948,  70:  1055 
  • 21a Nakamura T. Yorimitsu H. Shinokubo H. Oshima K. Bull. Chem. Soc. Jpn.  2001,  74:  747 
  • 21b Nakamura T. Yorimitsu H. Shinokubo H. Oshima K. Synlett  1999,  1415 
  • Unrelated to the radical reaction in water other researches are in progress to develop alternatives to tin compounds:
  • 22a Fujita K. Nakamura T. Yorimitsu H. Oshima K. J. Am. Chem. Soc.  2001,  123:  3137 
  • 22b Mikami S. Fujita K. Nakamura T. Yorimitsu H. Shinokubo H. Matsubara S. Oshima K. Org. Lett.  2001,  3:  1853 
  • 23a Yorimitsu H. Shinokubo H. Oshima K. Chem. Lett.  2000,  104 
  • 23b Yorimitsu H. Shinokubo H. Oshima K. Bull. Chem. Soc. Jpn.  2001,  74:  225 
  • 24a Barton DHR. Jang DO. Jaszberenyi JC. J. Org. Chem.  1993,  58:  6838 
  • 24b Barton DHR. Jang DO. Jaszberenyi JC. Tetrahedron Lett.  1992,  33:  5709 
  • 25a McCague R. Pritchard RG. Stoodley RJ. Williamson DS. Chem. Commun.  1998,  2691 
  • 25b Graham SR. Murphy JA. Coates D. Tetrahedron Lett.  1999,  40:  2414 
  • 25c Tokuyama H. Yamashita T. Reding MT. Kaburagi Y. Fukuyama T. J. Am. Chem. Soc.  1999,  121:  3791 
  • 25d Reding MT. Fukuyama T. Org. Lett.  1999,  1:  973 
  • 25e Martin CG. Murphy JA. Smith CR. Tetrahedron Lett.  2000,  41:  1833 
  • 25f Graham AE. Thomas AV. Yang R. J. Org. Chem.  2000,  65:  2583 
  • 25g Murphy JA. Pure Appl. Chem.  2000,  72:  1327 
  • 25h Murphy JA. Scott KA. Sinclair RS. Martin CG. Kennedy AR. Lewis N. J. Chem. Soc., Perkin Trans. 1  2000,  2395 
  • 25i Kita Y. Nambu H. Ramesh NG. Anilkumar G. Matsugi M. Org. Lett.  2001,  3:  1157 
  • 25j Jang DO. Song SH. Tetrahedron Lett.  2000,  41:  247 
  • 26 Jang DO. Tetrahedron Lett.  1996,  37:  5367 
  • Environmentally benign approach with radical reactions in ethanol:
  • 27a Yamazaki O. Togo H. Matsubayashi S. Yokoyama M. Tetrahedron  1999,  55:  3735 
  • 27b Yamazaki O. Togo H. Matsubayashi S. Yokoyama M. Tetrahedron Lett.  1998,  39:  1921 
  • 28 Usugi S. Yorimitsu H. Oshima K. Tetrahedron Lett.  2001,  42:  4535 
  • 29a Li C.-J. Chan T.-H. Tetrahedron Lett.  1991,  32:  7017 
  • 29b Araki S. Jin SJ. Idou Y. Butsugan Y. Bull. Chem. Soc. Jpn.  1992,  65:  1736 
  • 31a Yang D. Ye X.-Y. Gu S. Xu M. J. Am. Chem. Soc.  1999,  121:  5579 
  • 31b Yang D. Ye X.-Y. Xu M. Pang K.-W. Cheung KK. J. Am. Chem. Soc.  2000,  122:  1658 ; See also Ref.19
30

Unpublished result.

32

Yorimitsu, H.; Oshima, K. Bull. Chem. Soc. Jpn. 2002, 75, in press.