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Synlett 2004(6): 987-990  
DOI: 10.1055/s-2004-822884
LETTER
© Georg Thieme Verlag Stuttgart · New York

Radical Chain Reaction of Benzenethiol with Pentynylthiol Esters: Production of Aldehydes under Stannane/Silane-Free Conditions

Luisa Benati*, Rino Leardini, Matteo Minozzi, Daniele Nanni, Rosanna Scialpi, Piero Spagnolo*, Giuseppe Zanardi
Dipartimento di Chimica Organica ‘A. Mangini’, Viale Risorgimento 4, 40136 Bologna, Italy
Fax: +39(051)2093654; e-Mail: spagnolo@ms.fci.unibo.it;
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Publication History

Received 12 February 2004
Publication Date:
25 March 2004 (online)

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Abstract

The radical chain reaction of benzenethiol with accessible 4-pentynylthiol esters provides a new stannane/silane-free protocol for the production of aromatic and aliphatic aldehydes. The procedure is especially useful for the aryl and primary aldehydes, even in the presence of substituents highly sensitive to reductive conditions, and is also of some utility for the vinylic and secondary ones. The protocol is instead not applicable to the tertiary aldehydes, owing to preferential alkane-forming decarbonylation, although the tertiary ones derived from bridgehead precursors can still be usefully produced.

Key words

acyl radicals - reduction - aldehydes - benzenethiol - thiol esters

    References

  • For recent reviews on the chemistry of acyl radicals and their application in synthesis, see:
  • 1a Ryu I. Sonoda N. Angew. Chem., Int. Ed. Engl.  1996,  35:  1050 
    CrossrefPubMedGoogle Scholar
  • 1b Ryu I. Sonoda N. Curran DP. Chem. Rev.  1996,  96:  177 
    CrossrefPubMedGoogle Scholar
  • 1c Chatgilialoglu C. Crich D. Komatsu M. Ryu I. Chem. Rev.  1999,  99:  1991 
    CrossrefPubMedGoogle Scholar
  • 2 Benati L. Leardini R. Minozzi M. Nanni D. Spagnolo P. Strazzari S. Zanardi G. Org. Lett.  2002,  4:  3079 ; and references therein
    CrossrefGoogle Scholar
  • For very recent productions of acyl radicals by oxidation of acyl hydrazine precursors see:
  • 3a Braslau R. Anderson MO. Rivera F. Jimenez A. Haddad T. Axon JR. Tetrahedron  2002,  58:  5513 
    CrossrefGoogle Scholar
  • 3b Bath S. Laso NM. Lopez-Ruiz H. Quiclet-Sire B. Zard SZ. Chem. Commun.  2003,  204 
    CrossrefGoogle Scholar
  • For very recent examples of the use of selenoesters in acyl radical chemistry see:
  • 4a Allin SM. Barton WRS. Bowman WR. McInally T. Tetrahedron Lett.  2001,  42:  7887 
    CrossrefGoogle Scholar
  • 4b Bennasar M.-L. Roca T. Griera R. Bosch J. Org. Lett.  2001,  3:  1697 
    CrossrefGoogle Scholar
  • 4c Bennasar M.-L. Roca T. Griera R. Bassa M. Bosch J. J. Org. Chem.  2002,  67:  6268 
    CrossrefGoogle Scholar
  • 5 For a peculiar use of thiol esters in acyl radical chemistry see: Ozaki S. Yoshinaga H. Matsui E. Adachi M. J. Org. Chem.  2001,  66:  2503 
    CrossrefGoogle Scholar
  • 6a Crich D. Yao Q. J. Org. Chem.  1996,  61:  3566 
    CrossrefGoogle Scholar
  • 6b Crich D. Hao X. J. Org. Chem.  1997,  62:  5982 
    CrossrefGoogle Scholar
  • 7 Benati L. Calestani G. Leardini R. Minozzi M. Nanni D. Spagnolo P. Strazzari S. Org. Lett.  2003,  5:  1313 
    CrossrefGoogle Scholar
  • 8 Smith MB. March J. In Advanced Organic Chemistry-Reactions, Mechanisms and Structures   5th ed.:  Wiley-Interscience; New York: 2001.  p.532-533  
    Google Scholar
  • 9a Ballestri M. Cardi N. Chatgilialoglu C. Sommazzi A. Tetrahedron Lett.  1992,  33:  1787 
    CrossrefGoogle Scholar
  • 9b Chatgilialoglu C. Lucarini M. Tetrahedron Lett.  1995,  36:  1299 
    CrossrefGoogle Scholar
  • 9c Chatgilialoglu C. Ferreri C. Lucarini M. Pedrielli P. Pedulli GF. Organometallics  1995,  14:  2672 
    CrossrefGoogle Scholar
  • 10a Graf W. Heuberger C. Pfenninger J. Helv. Chim. Acta  1980,  63:  2328 
    CrossrefGoogle Scholar
  • 10b Graf W. Pfenninger J. Helv. Chim. Acta  1980,  63:  1562 
    CrossrefGoogle Scholar
  • 11 Penn JH. Liu F. J. Org. Chem.  1994,  59:  2608 
    CrossrefGoogle Scholar
  • 12 An acyl radical abstracts a hydrogen from PhSH ca. 100 and 2500 times faster than from Bu3SnH and (TMS)3SiH, respectively; see: Brown CE. Neville AG. Rayner DM. Ingold KU. Lusztyk J. Aus. J. Chem.  1995,  48:  363 ; and ref. 9b,c
    Google Scholar
  • 15a Merrill SH, and Unruh CC. inventors; Brit. Patent No.  843.541.  ; Chem. Abstr. 1963, 59, 2994d
    Crossref
  • 15b Walton C. Lahti PM. Synth. Commun.  1998,  28:  1087 
    CrossrefGoogle Scholar
  • 15c Heck RF. Org. Synth.  1971,  51:  17 
    CrossrefGoogle Scholar
  • 15d Takeuchi K. Kitagawa I. Akiyama F. Shibata T. Kato M. Okamoto K. Synthesis  1987,  612 
    CrossrefGoogle Scholar
  • 15e Polonski T. J. Chem. Soc., Perkin Trans. 1  1983,  305 
    CrossrefGoogle Scholar
  • 16a Montevecchi PC. Navacchia ML. Spagnolo P. Tetrahedron Lett.  1997,  38:  7913 
    CrossrefGoogle Scholar
  • 16b Montevecchi PC. Navacchia ML. Spagnolo P. Eur. J. Org. Chem.  1998,  1219 
    CrossrefGoogle Scholar
  • 16c Kim S. Joe GH. Do JY. J. Am. Chem. Soc.  1993,  115:  3328 
    CrossrefGoogle Scholar
  • 16d Kim S. Joe GH. Do JY. J. Am. Chem. Soc.  1994,  116:  5521 
    CrossrefGoogle Scholar
  • 16e Benati L. Bencivenni G. Leardini R. Minozzi M. Nanni D. Rizzoli C. Scialpi S. Spagnolo P. Zanardi G. Org. Lett.  2004,  6:  417 ; and references therein
    CrossrefGoogle Scholar
13

General Procedure for the Preparation of Thiol Esters 1: To a stirred solution of 10 mmol of the appropriate acyl chloride, directly available or prepared by treatment of commercial or already known acid with SOCl2, and DMAP (1.6 g, 13 mmol) in CH2Cl2 (20 mL) was slowly added, at r.t. and under a stream of nitrogen, a solution of 4-pentyne-1-thiol (1 g, 10 mmol) [7] in CH2Cl2 (100 mL). The resulting mixture was stirred at r.t. for an additional 1-2 h, until disappearance of the thiol reagent (TLC), then treated with Et2O (100 mL) and eventually filtered. The organic filtrate was concentrated and the residue subjected to column chromatography. The title compounds were obtained in 60-80% yields and were characterized on the basis of 1H NMR and 13C NMR spectral data. Illustrative data for S-(4-pentynyl) 4-chlorobenzenecarbothiate(1b): 1H NMR (300 MHz, CDCl3): δ = 1.91 (m, 2 H, CH2), 2.01 (t, 1 H, alkynylic CH, J = 2.61 Hz), 2.34 (dt, 2 H, CH2, J 1 = 2.61 Hz, J 2 = 6.95 Hz), 3.20 (t, 2 H, CH2, J = 6.95 Hz), 7.43 (m, 2 H, aromatic CH), 7.91 (m, 2 H, aromatic CH). 13C NMR (75 MHz, CDCl3): δ = 17.82 (CH2), 28.13 (CH2), 28.44 (CH2), 69.50 (CH), 83.13 (C), 128.71 (CH), 129.07 (CH), 135.51 (C), 139.91 (C), 190.64 (CO).

14

General Procedure for the Reactions of Thiol Esters 1 with Benzenethiol: A benzene (20 mL) solution of PhSH (2.2 mmol) and AIBN (0.4 mmol) was added by a syringe pump over ca. 3 h to a refluxing solution of the appropriate thiol ester (2 mmol) in degassed benzene (30 mL) under a nitrogen atmosphere. The resultant mixture was refluxed for an additional 2-3 h until the virtual disappearance of the starting substrate (TLC). After cooling to r.t., the solvent was removed in vacuo and the residue subjected to chromatographic separation on silica gel by progressive elution with light petroleum/Et2O mixtures. The aldehydes 4a-c,f-h,k, as well as the alkanes 5-7, were commercial products. The known aldehydes 4d, [15a] 4e, [15b] 4j, [15c] 4l, [15d] and 4m [15e] were characterized by 1H NMR and 13C NMR spectral data. The vinyl sulfides 3a-h,j-m were generally obtained as an inseparable mixtures of the E- and Z-isomer.

17

Previous attempts to obtain 2-hexenal by photochemical homolysis of (S)-2-naphthyl-2-hexenethioate resulted in extensive formation of reduced hexanal: see ref. [11]

18

When the same azidoalkanoyl radical was generated by the method of Crich, in the presence of Bu3SnH, the production of aldehyde 4i was totally suppressed in favor of decarbonylated and lactam product: see ref. [2]

19

1-Adamantanecarbonyl chloride is totally converted into adamantane upon radical reaction with (TMS)3SiH at 80 °C: see ref. [9a]

20

The amount of the resulting vinyl sulfide adduct 3 was not significantly diminished when an alkanethiol such as methyl thioglycolate was used in place of benzenethiol.