A Simple and Practical Approach to α-Halo- and α-Phenylthio-α,β-Enones

Abstract

α-Halo-α,β-unsaturated ketones and α-thio-α,β-unsaturated ketones were prepared from readily accessible allenolates. The allenolates were formed in situ by a carbamoyl group migration.

Key words

allenes - carbanions - halogenations - enones - cross-coupling­

References

• 2 Larock LC. Comprehensive Organic Transformations   2nd ed.:  Wiley-VCH; New York: 1999.  p.715 
• 3a Diederich F. Stang PJ. Metal Catalyzed Cross-Coupling Reactions   Wiley-VCH; Weinheim: 1998. 
• 3b Negishi E.-I. de Meijere A. Handbook of Organopalladium Chemistry for Organic Synthesis   Wiley; New York: 2002. 
• 4a Johnson CR. Braun MP. J. Am. Chem. Soc.  1993,  115:  11014 
• 4b Johnson CR. Harikrishnan LS. Golebiowski A. Tetrahedron Lett.  1994,  35:  7735 
• 4c Johnson CR. Adams JP. Collins MA. J. Chem. Soc., Perkin Trans. 1  1993,  1 
• 5a Kowalski CJ. Weber AE. Fields KW. J. Org. Chem.  1982,  47:  5088 
• 5b Benhida R. Blanchard P. Fourrey J.-L. Tetrahedron Lett.  1998,  39:  6849 
• 5c Dieter RK. Nice LE. Velu SE. Tetrahedron Lett.  1996,  37:  2377 
• 5d Righi G. Bovicelli P. Sperandio A. Tetrahedron Lett.  1999,  40:  5889 
• 5e Ley SV. Whittle AJ. Tetrahedron Lett.  1981,  22:  3301 
• 5f Shepherd RG. White AC. J. Chem. Soc., Perkin Trans. 1  1987,  2153 
• 6a Bovonsombat P. Angara GJ. McNelis E. Tetrahedron Lett.  1994,  35:  6787 
• 6b Johnson CR. Adams JP. Braun MP. Senanayake CBW. Wovkulich PM. Uskokovic MR. Tetrahedron Lett.  1992,  33:  917 
• 6c Sha C.-K. Huang S.-J. Tetrahedron Lett.  1995,  36:  6927 
• 7 Lee YR. Cho BS. Kwon HJ. Tetrahedron  2003,  59:  9333 
• 8a The Chemistry of Ketenes, Allenes and Related Compounds   Patai S. Wiley; Chichester: 1980. 
• 8b Schuster HF. Coppola GM. Allenes in Organic Synthesis   Wiley; New York: 1984. 
• 8c Landor SR. The Chemistry of the Allenes   Academic Press; New York: 1982. 
• 8d Hoffmann-Röder A. Krause N. Angew. Chem. Int. Ed.  2004,  43:  1196 ; Angew. Chem. 2004, 116, 1216
• 8e Zimmer R. Synthesis  1993,  165 
• 9 Schultz-Fademrecht C. Tius MA. Grimme S. Wibbeling B. Hoppe D. Angew. Chem. Int. Ed.  2002,  41:  1532 ; Angew. Chem. 2002, 114, 1610
• 10 Gudimalla N. Fröhlich R. Hoppe D. Org. Lett.  2004,  6:  4005 
• 13 Otwinowski Z. Minor W. Methods Enzymol.  1997,  276:  307 
• 14 Blessing RH. Acta Cryst.  1995,  A51:  33 
• 15 Blessing RH. J. Appl. Cryst.  1997,  30:  421 
• 16 Sheldrick GM. Acta Cryst.  1990,  A46:  467 
• 17 Sheldrick GM. SHELXL 97   University of Göttingen; Göttingen: 1997. 
• 18 Reich HJ. Eisenhart EK. Olson RE. Kelly MJ. J. Am. Chem. Soc.  1986,  108:  7791 
• 19a Mitchell TN. Synthesis  1992,  803 
• 19b Negishi E.-I. Lin F. Metal-Catalyzed Cross-Coupling Reactions   3rd ed.:  Wiley-VCH; Weinheim: 2001.  Chap. 1.
• 19c Palmisano G. Santagostino M. Helv. Chim. Acta  1993,  76:  2356 
• 19d Banwell MG. Kelly BD. Kokas OJ. Lupton DW. Org. Lett.  2003,  5:  2497 

1

X-ray structure analysis.

11

In this case, the reaction mixture was stirred to room temperature.

12

Data set was collected with a Nonius KappaCCD diffractometer. COLLECT (Nonius B. V., 1998), data reduction: DenzoSMN, [13] absorption correction data: SORTAV, [14] [15] structure solution: SHELXS-97, [16] structure refinement: SHELXL-97, [17] and graphics: SCHAKAL (E. Keller). Crystallographic data (excluding structure factors) for the structures reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication CCDC-249195. Copies of the data can be obtained free of charge on application to The Director, CCDC, 12, Union Road, Cambridge CB2 1EZ, UK [fax: [phone], e-mail: [e-mail]].