Synthesis of Phosphole-2,5-dicarboxylic Acids via a [1,5]-Shift of Carbon Dioxide around the Phosphole Nucleus

Organic Letters

Volumn 4, Issue 8, 2002, Pages 1245-1247

  Melaimi, Mohand ^a   Ricard, Louis ^a   Mathey, François ^a   Le Floch, Pascal ^a  

^a LABORATOIRE HÉTÉROÉLÉMENTS ET COORDINATION   (France)

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EID: 0242595605     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol0102895     Document Type: Article

References (16)

1. (a) Quin, L. D.; Quin, G. S. In Phosphorus-Carbon Heterocyclic Chemistry: The rise of a New Domain; Mathey, F., Ed.; Pergamon: Amsterdam, 2001; Chapter 4.2.2, p 307.
2. (b) Dillon, K. B.; Mathey, F.; Nixon, J. F. Phosphorus: The Carbon Copy; Wiley: Chichester, 1998; p 203.
3. (c) Quin, L. D. In Comprehensive Heterocyclic Chemistry; Katritzky, A. R., Rees, C. W., Scriven, E. F. V., Eds; Elsevier: Oxford, 1996; Vol. 2, p 757.
4. (d) Mathey, F. In Science of Synthesis; Maas, G., Ed.; Thieme: Stuttgart, 2001; Chapter 14, p 553.
5. (a) Deschamps, E.; Mathey, F. Bull. Soc. Chim. Fr. 1992, 129, 486.
6. (b) Deschamps, E.; Ricard, L.; Mathey, F. Angew. Chem., Int. Ed. Engl. 1994, 33, 1158.
7. (c) Deschamps, E.; Mathey, F. C. R. Acad. Sci., Paris, Ser. IIc 1998, 715.
8. (a) Holand, S.; Jeanjean, M.; Mathey, F. Angew. Chem., Int. Ed. Engl. 1997, 36, 98.
9. (b) Deschamps, B.; Mathey, F. Bull. Soc. Chim. Fr. 1996, 133, 541.
10. (c) Holand, S.; Maigrot, N.; Charrier, C.; Mathey, F. Organometallics 1998, 17, 2996.
11. (d) Toullec, P.; Mathey, F. Synlett 2001, 1977.
12. (a) Sava, X.; Maigrot, N.; Mézailles, N.; Ricard, L.; Mathey, F.; Le Floch, P. Organometallics 1999, 18, 4205.
13. (b) Westerhausen, M.; Digeser, M. H.; Gücjel, C.; Nöth, H.; Knizek, J.; Ponkwar, W. Organometallics 1999, 18, 2491.
14. Anion 1 was synthesized using a two-step sequence which involves a preliminary oxidative coupling of 1-trimethylsilylpropyne using zirconocene. For a general reference, see: Fagan, P. J.; Nugent, W. A. J. Am. Chem. Soc. 1988, 110, 7239.
15. Though phospholide anions are strongly delocalized, a significant amount of the negative charge resides at the P atom and electrophilic attacks always take place at this site. No example of attack at the α-carbon atoms has previously been reported in the literature.
16. 31P NMR, the electrophile (6.0 or 3.0 mmol for the synthesis of 10 and 11) was added. After 30 min of stirring, the reaction was completed and LiI (100 mmol) was added. After 12 h of stirring at room temperature, the solvent was evaporated and methanol (40 mL) and then TMSCl (18.0 mmol) were added. The resulting solution was stirred for 5 min, and Celite (2 g) was added. After evaporation of the solvent, the coated silica gel was dropped onto the top of a silica gel packed column for chromatography and the phosphole was eluted with methanol as eluent.