Convenient Synthesis of α,α-Difluorinated Carbonyl Compounds from Alkynes through a Fluoro-deboronation Process

Abstract

Catalytic diboration of alkynes towards alkenyl diboronates provides suitable intermediates that can be converted into α-fluorinated and α,α-difluorinated carbonyl compounds via electrophilic fluorination with Selectfluor.

Key words

alkynes - alkenyl diboronates - electrophilic fluorination - Selectfluor - α,α-difluoroketones

References

• 1a Brown HC. In Hydroboration   Wiley-Interscience; New York: 1962. 
• 1b Brown HC. In Boranes in Organic Chemistry   Cornell University Press; Ithaca: 1972. 
• 1c Brown HC. In Organic Synthesis via Boranes   Wiley-Interscience; New York: 1975. 
• 1d Pelter A. Smith K. Brown HC. In Borane Reagents   Academic Press; New York: 1988. 
• 2a Cragg GML. In Organoboranes in Organic Synthesis   Dekker; New York: 1973. 
• 2b Onak T. In Organoborane Chemistry   Academic Press; New York: 1975. 
• 3 Marder TB. Norman NC. Top. Catal.  1998,  5:  63 
• 4 Dembitsky VM. Abu Ali H. Srebnik M. Appl. Organomet. Chem.  2003,  17:  327 
• 5 Ishiyama T. Miyaura N. Chem. Rec.  2004,  3:  271 
• 6a Ishiyama T. Matsuda N. Miyaura N. Suzuki A. J. Am. Chem. Soc.  1993,  115:  11018 
• 6b Miyaura N. Suzuki A. Chem. Rev.  1995,  95:  2457 
• 6c Miyaura N. In Advances in Metal-Organic Chemistry   JAI; Stanford: 1998. 
• 6d Suzuki A. In Metal-Catalyzed Cross-Coupling Reactions   Wiley-VCH; Weinheim: 1998. 
• 7 Ishiyama T. Matsuda N. Murata M. Ozawa F. Suzuki A. Miyaura N. Organometallics  1996,  15:  713 
• 8 Lesley G. Nguyen P. Taylor NJ. Marder TB. Scott AJ. Clegg W. Norman NC. Organometallics  1996,  15:  5137 
• 9 Iveson CN. Smith MR. Organometallics  1996,  15:  5155 
• 10 Baker RT. Nguyen P. Marder TB. Westcott SA. Angew. Chem., Int. Ed. Engl.  1995,  34:  1336 
• 11 Thomas RL. Souza FES. Marder TB. J. Chem. Soc., Dalton Trans.  2001,  1650 
• 12 Mann G. John KD. Baker RT. Org. Lett.  2000,  2:  2105 
• 13 Ishiyama T. Yamamoto M. Miyaura N. Chem. Lett.  1996,  1117 
• 14a In Organofluorine Compounds in Medicinal Chemistry and Biomedical Applications   Filler R. Kobayashi Y. Yagupolskii LM. Elsevier; Amsterdam: 1993. 
• 14b In Fluorine Containing Amino Acids: Synthesis and Properties   Kukhar VP. Soloshonok VA. John Wiley and Sons; Chichester: 1995. 
• 14c In Biomedical Frontiers of Fluorine Chemistry   Ojima L. McCarthy JR. Welch JT. American Chemical Society; Washington DC: 1996. 
• 15a In Synthetic Fluorine Chemistry   Olah GA. Chambers RD. Prakash GKS. John Wiley and Sons; New York: 1992. 
• 15b Banks RE. Smart BE. Tatlow JC. In Organofluorine Chemistry: Principles and Commercial Applications   Plenum Press; New York: 1994. 
• 16 Welch JT. Eswarakrishnan S. In Fluorine in Bioorganic Chemistry   John Wiley and Sons; New York: 1991. 
• 17 Lal GS. Pez GP. Syvret RG. Chem. Rev.  1996,  96:  1737 
• 18 Prakash GKS. Hu J. Olah GA. J. Fluorine Chem.  2001,  112:  357 
• 19 Nyffeler PT. Gonzalez Durón S. Burkart MD. Vincent SP. Wong C.-H. Angew. Chem. Int. Ed.  2005,  44:  192 
• 20 Umemoto T. Fukami S. Tomizawa G. Harasawa K. Kawada K. Tomita K. J. Am. Chem. Soc.  1990,  112:  8563 
• 21 Lal GS. J. Org. Chem.  1993,  58:  2791 
• 22 Xu Z. DesMarteau DD. Gotoh Y. J. Chem. Soc., Chem. Commun.  1991,  179 
• 23 Banks RE. Lawrence JJ. Popplewell AL. J. Chem. Soc., Chem. Commun.  1994,  343 
• 24 Zupan M. Iskra J. Stavber S. J. Org. Chem.  1995,  60:  259 
• 25 Stavber S. Zupan M. Synlett  1996,  693 
• 26 Greedy B. Gouverneur V. Chem. Commun.  2001,  233 
• 27 Matthews DP. Miller SC. Jarvi ET. Sabol JS. McCarthy JR. Tetrahedron Lett.  1993,  34:  3057 
• 28 Petasis NA. Yudin AK. Zavialov IA. Prakash GKS. Olah GA. Synlett  1997,  606