Direct Preparation of Z-1,3-Enyne Systems with a TMS-Propargylic Sulfone: Application of a One-Pot Julia Olefination

Abstract

A benzothiazolyl TMS-propargylic sulfone was sub­jected to one-pot Julia olefinations with a variety of aliphatic and ­aromatic aldehydes. Predominant Z-selectivity up to 98:2 and good chemical yields were obtained in a facile route to the desired Z-1,3-enyne moieties.

Key words

enynes - olefination - aldehydes - propargylic sulfones - natural products

References and Notes

• 1a Negishi E. Anastasia L. Chem. Rev.  2003,  103:  1979 
• 1b Saito S. Yamamoto Y. Chem. Rev.  2000,  100:  2901 
• 2 Moriarty RM. Pavlović D. J. Org. Chem.  2004,  69:  5501 
• 3 Kaloko J. Hayford A. Org. Lett.  2005,  7:  4305 
• 4 Maloney KM. Danheiser RL. Org. Lett.  2005,  7:  3115 
• 5 López S. Fernández-Trillo F. Midón P. Castedo L. Saá C. J. Org. Chem.  2005,  70:  6346 
• 6a Maryanoff BE. Reitz AB. Chem. Rev.  1989,  89:  863 
• 6b Wittig G. Geissler G. Justus Liebigs Ann. Chem.  1953,  580:  44 
• 7a Van Staden LF. Gravestock D. Ager DJ. Chem. Soc. Rev.  2002,  31:  195 
• 7b Peterson DJ. J. Org. Chem.  1968,  33:  780 
• 8 Johnson CR. Shanklin JR. Kirchhoff RA. J. Am. Chem. Soc.  1973,  95:  6462 
• 9 Julia M. Paris J.-M. Tetrahedron Lett.  1973,  4833 
• 10a Blakemore PR. J. Chem. Soc., Perkin Trans. 1  2002,  2563 
• 10b Baudin JB. Hareau G. Julia SA. Lorne R. Ruel O. Bull. Soc. Chim. Fr.  1993,  130:  336 
• 10c Baudin JB. Hareau G. Julia SA. Lorne R. Ruel O. Bull. Soc. Chim. Fr.  1993,  130:  856 
• 10d Baudin JB. Hareau G. Julia SA. Ruel O. Tetrahedron Lett.  1991,  32:  1175 
• For recent reviews of the alkene-metathesis reaction, see:
• 11a Nicolaou KC. Bulger PG. Sarlah D. Angew. Chem. Int. Ed.  2005,  44:  4490 
• 11b Schmidt B. Hermanns J. Top. Organomet. Chem.  2004,  7:  223 
• 11c Fürstner A. Angew. Chem. Int. Ed.  2000,  39:  3012 
• 11d Grubbs RH. Chang S. Tetrahedron  1998,  54:  4413 
• For general reviews, see:
• 12a Nicolaou KC. Bulger PG. Sarlah D. Angew. Chem. Int. Ed.  2005,  44:  4442 
• 12b Negishi E.-I. Liu F. In Metal-Catalyzed Cross-Coupling Reactions   Diederich F. Stang PJ. Wiley-VCH; Weinheim: 1998.  p.1 
• 12c Farina V. Krishnamurthy V. Scott WJ. Org. React. (NY)  1997,  50:  1 
• 12d Miyaura N. Suzuki A. Chem. Rev.  1995,  95:  2457 
• 13 Sorg A. Brückner R. Synlett  2005,  289 
• 14 Bonini C. Chiummiento L. Videtta V. Synlett  2005,  3067 
• For other examples with high cis-selectivity during the one-pot Julia olefination of allyl benzothiazolyl sulfones with α,β-unsaturated aldehydes, see:
• 18a Furuichi N. Hara H. Osaki T. Mori H. Katsumura S. Angew. Chem. Int. Ed.  2002,  41:  1023 
• 18b Furuichi N. Hara H. Osaki T. Nakano M. Mori H. Katsumura S. J. Org. Chem.  2004,  69:  7949 
• 18c

  Ref. 13.

• 18d Vaz B. Alvarez R. Souto JA. de Lera AR. Synlett  2005,  294 
• 18e Vaz B. Alvarez R. Brückner R. de Lera AR. Org. Lett.  2005,  7:  545 
• 19 Smith AB. Freeze BS. LaMarche MJ. Hirose T. Brouard I. Xian M. Sundermann KF. Shaw SJ. Burlingame MA. Horwitz SB. Myles DC. Org. Lett.  2005,  7:  315 
• 22 Hayford A. Kaloko J. El-Kazaz S. Bass G. Org. Lett.  2005,  7:  2671 

15

Premetallated conditions: base added to sulfone, then aldehyde added.

16

Barbier conditions: base added to the mixture of sulfone and aldehyde.

17

Pent-2-ynyl BT-sulfone, reacting with benzaldehyde according to method A, afforded the corresponding enyne in only 18% yield but with 94:6 Z/E ratio.

20

Preparation of aldehyde 8f, starting from the alcohol 9 (Scheme [3] ). Alcohol 9 was prepared according to: Bonini, C.; Chiummiento, L.; Videtta, V.; Colobert, F.; Solladié, G., manuscript in preparation.

21

No β-elimination product was observed for aldehyde 8e. Moreover, the optical rotation for the unreacted aldehyde 8f shows the same the value of the starting aldehyde, thus indicating that no epimerization reaction occurs.