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2,3,4,5-tetramethylphosphole has been reported by Nief, et at.2 That procedure involved aluminum chloride - coupling of 2-butyne, followed by reaction with dichlorophenylphosphine to form a chlorophospholium tetrachloroaluminate which was then reduced with tributylphosphine to produce the phosphole in 68% yield.
Using a procedure similar to that described here, or using isolated zirconium metallacycles as reagents, we have been able to prepare not only phospholes, but also arsoles, stiboles, bismoles, siloles, germoles, stannoles, galloles, thiophenes, selenophenes, and borole Diels-Alder dimers.4 Since a number of other titanium and zirconium metallacycles are readily available,4 these reagents should be useful in the preparation of a variety of heterocycles.
1. E. I. du Pont de Nemours and Co., Inc., Central Research and Development Department, Experimental Station, Box 80328, E328/364, Wilmington, DE 19880-0328. Contribution No. 5123. We thank Ronald J. Davis for technical assistance.
2. Nief, F.; Mathey, F.; Ricard, L.; Robert, F. Organometallics 1988, 7, 921.
3. Mathey, F. Chem. Rev. 1988, 88, 429; Mathey, F. Phosphorus Sulfur 1983, 18, 101; Mathey, F.; Fischer, J.; Nelson, J. H. Struct. Bonding (Berlin) 1983, 55, 153; Mathey, F. In "Topics in Phosphorus Chemistry;" Grayson, M.; Griffith, E. J., Eds.; Wiley: New York, 1980; Vol. 10, p. 1-128.
4. Fagan, P. J.; Nugent, W. A. J. Am. Chem. Soc. 1988, 110, 2310; Fagan, P. J.; Bums, E. G.; Calabrese, J. C. J. Am. Chem. Soc. 1988, 110, 2979; RajanBabu, T. V.; Nugent, W. A.; Taber, D. F.; Fagan, Paul, J. J. Am. Chem. Soc. 1988, 110, 7128; Buchwald, S. L.; Watson, B. T.; Lum, R. T.; Nugent, W. A. J. Am. Chem. Soc. 1987, 109, 7137.
5. Negishi, E.-i.; Cederbaum, F. E.; Takahashi, T. Tetrahedron Lett. 1986, 27, 2829.
Chemical Abstracts Nomenclature (Collective Index Number); (Registry Number)
1-Phenyl-2,3,4,5-tetramethylphosphole: 1H-Phosphole, 2,3,4,5-tetramethyM-phenyl-(12); (112549-07-2)
Zirconocene dichloride: Zirconium, dichloro-7t-cyclopentadienyl- (8); Zirconium, dichlorobis(ri5-2,4-cyclopentadien-1-yl)- (9); (1291-32-3)
2-Butyne (8,9); (503-17-3)
Dichlorophenylphosphine: Phosphonous dichloride, phenyl- (8,9); (644-97-3)
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2551R* 2552R* 2571*
Y. Naruta, Y. Nishigaichi, and K. Maruyama, Department of Chemistry, Faculty of Science, Kyoto University, Sakyo-ku, Kyoto 606, Japan
Y. Naruta and K. Maruyama, Department of Chemistry, Faculty of Science, Kyoto University, Sakyo-ku, Kyoto 606, Japan
T. F. Jamison, W. D. Lubell, J. M. Dener, M. J. Krische and H. Rapoport, Department of Chemistry, University of California, Berkeley, CA 94720
Benzoannelation of Ketones.
M. A. Tius and G. S. K. Kannangara, Department of Chemistry, The University of Hawaii, Honolulu, Hawaii 96822
3-(1 -Octen-1 -yl)cyclopentanone.
R. C. Sun, M. Okabe, D. L. Coffen, and J. Schwartz, Chemistry Research Department, Hoffmann-La Roche Inc., Nutley, NJ 07110
Asymmetric Hydrogenation of Allylic Alcohols Using BINAP-Ruthenium Complexes: (S)-(-)-Citronellol.