Synthesis and Intramolecular Cyclization of Diethylphosphono-Substituted Allenic Glycols

Abstract

This paper describes a convenient and efficient synthesis of new (2R)-5-substituted-5-(diethylphosphono)-penta-3,4-dien-1,2-diols. Phosphorylated allenic glycols are stable enough compounds, but under basic conditions they cyclized to (3R)-5-(3-hydroxy-2,3-dihydrofuryl)(diethylphosphono)alkanes through intramolecular nucleophilic addition of the terminal alkoxide to the central carbon atom of the allene system. Treatment of (3R)-5-(3-hydroxy-2,3-dihydrofuryl)(diethylphosphono)alkanes with a catalytic amount of p-toluenesulfonic acid in chloroform at 40-45 °C for 0.5 hours afforded diethylphosphono(2-furyl)alkanes.

Key words

cyclization - furans - 2,3-dihydrofurans - phosphaallenes - phosphorus heterocycles

References

• 1a Claesson A. Olsson L.-I. In The Chemistry of Allenes   Vol. 3:  Landor SR. Academic Press; London: 1982.  p.737 
• 1b Fuks R. Viehe HG. In The Chemistry of Acetylenes   Viehe HG. Marcel Dekker; New York: 1969.  p.425 
• 1c Padwa A. Meske M. Ni Z. Tetrahedron  1995,  51:  89 
• 2a Marshall JA. Sehon CA. J. Org. Chem.  1994,  59:  7169 
• 2b Walkup RD. Kim SW. J. Org. Chem.  1994,  59:  7169 
• 3a Claesson A. Olsson L.-I. In The Chemistry of Allenes   Vol. 2:  Landor SR. Academic Press; London: 1982.  p.369 
• 3b Nikam SS. Chu K.-H. Wang KK. J. Org. Chem.  1986,  51:  745 
• 3c Ma S. Shi Z. J. Org. Chem.  1998,  63:  6387 
• 3d Marshall JA. Yu B.-C. J. Org. Chem.  1994,  59:  324 
• 3e Hormuth S. Reissig H.-U. J. Org. Chem.  1994,  59:  67 
• 4a Marshall JA. Sehon CA. J. Org. Chem.  1995,  60:  5967 
• 4b Marshall JA. Bartley GS. Wallace EM. J. Org. Chem.  1996,  61:  5729 
• 5 Pravia K. White R. Fodda R. Maynard DF. J. Org. Chem.  1996,  61:  6931 
• 6 Brel VK. Synthesis  1999,  463 
• 7a Brel VK. Synth. Commun.  1999,  29:  3869 
• 7b Alabugin IV. Brel VK. Phosphorus, Sulfur and Silicon  1996,  1:  61 
• 7c Alabugin IV. Brel VK. Usp. Khim.  1997,  66:  225 
• 8a Brel VK. Abramkin EV. Chekhlov AN. Martynov IV. Dokl. Akad. Nauk SSSR  1990,  312:  619 
• 8c Brel VK. Synthesis  1998,  710 
• 8d Zefirov NS. Koz"min AS. Kasumov TM. Potekhin KA. Sorokin VD. Brel VK. Abramkin EV. Struchkov YT. Zhdankin VV. Stang PJ. J. Org. Chem.  1992,  57:  2433 
• 9 Schmid CR. Bryant JD. Dowlatzedah M. Phillips JL. Prather DE. Schantz RD. Sear NL. Vianco CS. J. Org. Chem.  1991,  56:  4056 
• 10 Chittenden GJF. Carbohydr. Res.  1980,  84:  350 
• 11 Zhong Y.-L. Shing TKM. J. Org. Chem.  1997,  62:  2622 
• 12 Brandsma L. Preparative Acetylenic Chemistry   Elsevier; Amsterdam: 1988.  p.265 
• 13 Mark V. In Mechanism of Molecular Migrations   Vol. 3:  Thyagajaran BS. Wiley; New York: 1969.  p.320-431  
• 14 Wolfgang R. In The Chemistry of Allenes   Vol. 2:  Landor SR. Academic Press; London: 1982.  p.832-847  
• 15 Langlois N. Choudhury PK. Tetrahedron Lett.  1999,  40:  2525 
• 16 Perrin DD. Armarego WLF. Perin DR. Purification of Laboratiry Chemicals   Pergamon Press; New York: 1980.