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.

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.