Synthesis 2010(22): 3811-3821  
DOI: 10.1055/s-0030-1258259
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

2-Benzothiazolyl Propargyl Sulfides: Versatile Precursors for Enantiopure Allenes, E-α,β-Unsaturated Ketones and Z-Sulfonylalkenes

Dagmar C. Kapeller*, Philip J. Kocienski*
School of Chemistry, University of Leeds, Leeds LS2 9JT, UK
Fax: +44(113)3436401; e-Mail: P.J.Kocienski@leeds.ac.uk; e-Mail: Dagmar.Kapeller@gmx.at;
Further Information

Publication History

Received 30 June 2010
Publication Date:
22 September 2010 (eFirst)

Abstract

A novel, stereospecific route to allenes is described. The approach proceeds via a retro-ene reaction, initiated by lithium aluminium hydride mediated cleavage of benzothiazole from the respective (chiral) 2-benzothiazolyl propargyl sulfone precursors. As such, allenes in up to 92% yield are formed under evolution of sulfur dioxide at ambient temperature. Furthermore, a new and mild way to generate E-α,β-unsaturated ketones has been discovered. These substrates are formed in around 50% yield by treating 2-benzothiazolyl propargyl sulfides with hydrogen peroxide and a catalytic amount of ammonium molybdate at room temperature. In the course of this research it was also found that treatment of 2-benzothiazolyl propargyl sulfones with sodium borohydride led to reduction of the triple bond exclusively to the Z-double bond.

    References

  • 1a Zimmer R. Synthesis  1993,  165 
  • 1b Guzmán-Durán A. Guzmán E. Pannell KH. Lloyd WD. Synth. Commun.  2003,  33:  3271 
  • 1c Hofmann-Röder A. Krause N. Angew. Chem. Int. Ed.  2004,  43:  1196 ; Angew. Chem. 2004, 116, 1216
  • 1d Kimura H. Fujiwara T. Katoh T. Nishide K. Kajimoto T. Node M. Chem. Pharm. Bull.  2006,  54:  399 
  • 1e Sabot C. Bérard D. Canesi S. Org. Lett.  2008,  10:  4629 
  • 2a Schuster HF. Coppola GM. In Allenes in Organic Synthesis   Wiley; New York: 1984. 
  • 2b Harrington PE. Tius MA. Org. Lett.  2000,  2:  2447 
  • 2c Wurz RP. Fu GC. J. Am. Chem. Soc.  2005,  127:  12234 
  • 2d Nishina N. Yamamoto YJ. Angew. Chem. Int. Ed.  2006,  45:  3314 ; Angew. Chem. 2006, 118, 3392
  • 3a Schultz-Fademrecht C. Wibbeling B. Fröhlich R. Hoppe D. Org. Lett.  2001,  3:  1221 
  • 3b Hofmann-Röder A. Krause N. Angew. Chem. Int. Ed.  2002,  41:  2933 ; Angew. Chem. 2002, 114, 3057
  • 3c Krause N. Hofmann-Röder A. Tetrahedron  2004,  60:  11671 
  • 3d Brummond KM. DeForrest JE. Synthesis  2007,  795 
  • 3e Ruano JLG. Marcos V. Alemán J. Angew. Chem. Int. Ed.  2008,  47:  6836 ; Angew. Chem. 2008, 120, 6942
  • 3f Ogasawara M. Tetrahedron: Asymmetry  2009,  20:  259 
  • 4 Frantz DE. Fässler R. Carreira EM. J. Am. Chem. Soc.  2000,  122:  1806 
  • 5a Matsumura K. Hashiguchi S. Ikariya T. Noyori R.
    J. Am. Chem. Soc.  1997,  119:  8738 
  • 5b Marshall JA. Eidam P. Schenck Eidam H. Org. Synth.  2007,  84:  120 
  • 6a Baudin J.-B. Julia SA. Ruel O. Wang Y. Tetrahedron Lett.  1990,  31:  213 
  • 6b Baudin J.-B. Julia SA. Lorne R. Bull. Soc. Chim. Fr.  1992,  129:  440 
  • 6c Baudin J.-B. Julia SA. Wang Y. Bull. Soc. Chim. Fr.  1995,  132:  754 
  • 6d Baudin J.-B. Julia SA. Bull. Soc. Chim. Fr.  1995,  132:  952 
  • 6e Braverman S. In The chemistry of sulfinic acids, esters and their derivatives. Rearrangements   Patai S. Wiley; Chichester: 1990.  p.297 
  • 6f Braverman S. Cherkinsky M. Top. Curr. Chem.  2007,  275:  67 
  • 6g Chochrek P. Wicha J. Eur. J. Org. Chem.  2007,  2534 
  • 6h Hopf H. Naujoks E. Tetrahedron Lett.  1988,  29:  609 
  • 7a Mitsunobu O. Synthesis  1981, 
  • 7b Hughes DL. Org. React.  1992,  42:  335 
  • 8 Bonini C. Chiummiento L. Videtta V. Synlett  2005,  3067 
  • 9 Sorg A. Brückner R. Synlett  2005,  289 
  • 10a Tang R. Mislow K. J. Am. Chem. Soc.  1970,  92:  2100 
  • 10b Evans DA. Andrews GC. J. Am. Chem. Soc.  1972,  94:  3672 
  • 11a Majumdar KC. Thyagarajan BS. J. Chem. Soc., Chem. Commun.  1972,  83 
  • 11b Majumdar KC. Ghosh SK. Tetrahedron Lett.  2002,  43:  2123 
  • 11c Aoyagi S. Makabe M. Shimada K. Takikawa Y. Kabuto C. Tetrahedron Lett.  2007,  48:  4639 
  • 12a Adam W. Chan Y.-Y. Cremer D. Gauss J. Scheutzow D. Schindler M. J. Org. Chem.  1987,  52:  2800 
  • 12b Birsa ML. Hopf H. Synlett  2007,  2753 
  • 13 Ueno J. Kojima A. Okawara M. Chem. Lett.  1984,  2125 
  • 15 Kar M. Basak A. Chem. Commun.  2006,  3818 
  • 16 Sheldrake HM. Wallace TW. Tetrahedron Lett.  2007,  48:  4407 
  • 17 Lipton MF. Sorenson CM. Sadler AC. Shapiro RH. J. Organomet. Chem.  1980,  186:  155 
  • 18 Lettan RB. Scheidt KA. Org. Lett.  2005,  7:  3227 
  • 19 Blakemore PR. Kocienski PJ. Marzcak S. Wicha J. Synthesis  1999,  1209 
  • 20 Carroll L. McCullough S. Rees T. Claridge TDW. Gouverneur V. Org. Biomol. Chem.  2008,  6:  1731 
  • 21 Gershock TJ. Johns DM. Noguchi Y. Williams RM. Org. Lett.  2008,  10:  613 
14

X-ray crystallographic data for 17a have been deposited at the Cambridge Crystallographic Data Centre. CCDC 781560 contains the supplementary crystallographic data for this paper and these data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif