A highly efficient synthesis of triisopropylsilyldifluorobromopropyne yields a versatile gem-difluoromethylene building block

Chemical Communications

Volumn , Issue 24, 1999, Pages 2545-2546

  Wang, ZhiGang ^a   Hammond, Gerald B ^a  

^a UNIVERSITY OF MASSACHUSETTS DARTMOUTH   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

BROMINE DERIVATIVE; FLUORINE DERIVATIVE;

ARTICLE; CATALYSIS; CHEMICAL MODIFICATION; CHEMICAL REACTION; OXIDATION REDUCTION REACTION; REACTION ANALYSIS; SYNTHESIS;

EID: 0033592885     PISSN: 13597345     EISSN: None     Source Type: Journal    
DOI: 10.1039/a907784g     Document Type: Article

References (24)

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2. For a recent leading reference see: K. Uneyama, G. Mizutani, K. Maeda and T. Kato, J. Org. Chem., 1999, 64, 6717. For a recent review see: M. J. Tozer and T. F. Herpin, Tetrahedron, 1996, 52, 8619.
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11. E. A. Hallinan and J. Fried, Tetrahedron Lett., 1984, 25, 2301. Also: T. Taguchi, O. Kitagawa, Y. Suda, S. Ohkawa, A. Hashimoto, Y. Iitaka and Y. Kobayashi, Tetrahedron Lett., 1988, 29, 5291 and references therein; S. Mcharek, S. Sibille, J. Y. Nedelec and J. Perichon, J. Organomet. Chem., 1991, 401, 211; J. M. Altenburger and D. Schirlin, Tetrahedron Lett., 1991, 32, 7255; J. M. Andres, M. A. Martinez, R. Pedrosa and A. Perez-Encabo, Synthesis, 1996, 1070.
12. E. A. Hallinan and J. Fried, Tetrahedron Lett., 1984, 25, 2301. Also: T. Taguchi, O. Kitagawa, Y. Suda, S. Ohkawa, A. Hashimoto, Y. Iitaka and Y. Kobayashi, Tetrahedron Lett., 1988, 29, 5291 and references therein; S. Mcharek, S. Sibille, J. Y. Nedelec and J. Perichon, J. Organomet. Chem., 1991, 401, 211; J. M. Altenburger and D. Schirlin, Tetrahedron Lett., 1991, 32, 7255; J. M. Andres, M. A. Martinez, R. Pedrosa and A. Perez-Encabo, Synthesis, 1996, 1070.
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18. 2Br: C, 46.33; H, 6.75. Found: C, 46.91 ; H, 6.83%). The triisopropylsilylacetylene starting material, purchased from GFS Co., contained diisopropylpropenylsilylacetylene (11%) and diisopropylpropylsilylacetylene (14%). Fractional distillation did not remove these impurities. The GC-MS analysis of 1 shows all three components were alkylated and their ratios perfectly match that of the starting material. The calculated C% and H% were based on the formula of triisopropylsilyldifluorobromopropyne. If the two impurities are removed from the calculation, the values found for C% and H% are 46.84 and 6.67%, respectively.
19. For a recent review of the TIPS group in organic chemistry see: C. Rücker, Chem. Rev., 1995, 95, 1009.
20. Similarly, whereas ynolates lack convenient methods for their generation a lithium silylynolate has been used in ketenylation reactions: H. Kai, K. Iwamoto, N. Chatani and S. Murai, J. Am. Chem. Soc., 1996, 118, 7634.
21. +, 5),170 (3), 159(2), 133 (100), 115 (30), 77 (26), 55 (46).
22. The major by-product is 3, an indication that, compared to the bromide, the triisopropylsilyldifluoropropyne anion is a better leaving group. For a leading reference on fluorinated phosphate mimics, see: D. O'Hagan and H. S. Rzepa, Chem. Commun., 1997, 645.
23. W. C. Sun, C. S. Ng and G. D. Prestwich, J. Org. Chem., 1992, 57, 132.
24. 2 will most likely limit its use in large-scale synthesis.