An Improved Suzuki-Miyaura Cross-Coupling Reaction for the Synthesis of Fluorine-Substituted 3-Biaryl-1-ferrocenyl-2-propen-1-one

Abstract

We studied the Pd(0)-catalyzed Suzuki-Miyaura cross-coupling reaction and obtained an improved procedure with shorter reaction times and higher conversions.

We investigated two methods stepwise addition of reagents and addition of all the reagents at the same time. We found that the reaction rate of the former is faster than the latter. Methanol was shown to be the optimum solvent for the reaction, however with an alcohol as the solvent the reaction was complete in under 1.5 hours. This improved methodology was applied to the synthesis of novel fluorine-substituted 3-biaryl-1-ferrocene-propene-1-ones, which were synthesized in good yields.

Suzuki cross-coupling reaction - Pd(0) catalyst - alcohol solvents - ferrocene derivatives - biaryl

References

<A NAME="RF07105SS-1A">1a</A> Balavoine GGA. Daran J.-C. Iftime G. Lacroix PG. Manoury E. Delaire JA. Maltey-Fanton I. Nakatani K. Di Bella S. Organometallics  1999,  18:  109 

<A NAME="RF07105SS-1B">1b</A> Diéguez M. Collomb M.-N. Crabtree RH. J. Organomet. Chem.  2000,  608:  146 

<A NAME="RF07105SS-1C">1c</A> Mata JA. Falomir E. Llusar R. Peris E. J. Organomet. Chem.  2000,  616:  80 

<A NAME="RF07105SS-1D">1d</A> Mata JA. Uriel S. Llusar R. Peris E. Organometallics  2000,  19:  3797 

<A NAME="RF07105SS-2">2</A> Imrie C. Loubser C. J. Chem. Soc., Perkin Trans. 2  1997,  399 

<A NAME="RF07105SS-3">3</A> Stepnicka P. Gyepes R. Lavastre O. Dixneuf PH. Organometallics  1997,  16:  5089 

<A NAME="RF07105SS-4A">4a</A> Long NJ. Martin AJ. Viler R. White AJP. Williams DJ. Younus M. Organometallics  1999,  18:  4261 

<A NAME="RF07105SS-4B">4b</A> Yu CJ. Chong Y. Kayyem JF. Gozin M. J. Org. Chem.  1999,  64:  2070 

<A NAME="RF07105SS-5">5</A> Peter M. Lammertink RGH. Vancso GJ. Hempenins MA. Van Os M. Knoll W. Beulen MWJ. Reinhoudt DN. Chem. Commun.  1999,  359 

<A NAME="RF07105SS-6">6</A> Iyoda M. Okobe T. Katada M. Kuwatani Y. J. Organomet. Chem.  1996,  569:  225 

<A NAME="RF07105SS-7A">7a</A> Green MLH. Green SR. Thompson ME. Bandy JA. Bloor D. Konlinsky PV. Jones RJ. Nature (London)  1987,  330:  360 

<A NAME="RF07105SS-7B">7b</A> Calabrese JC. Cheng LT. Green JC. Marder SR. Tam W. J. Am. Chem. Soc.  1991,  113:  7227 

<A NAME="RF07105SS-8">8</A> Rodríguez J.-G. Pleite S. J. Organomet. Chem.  2001,  637:  230 

<A NAME="RF07105SS-9A">9a</A> Song Q.-B. Lin R.-X. Shen T.-H. Synth. Commun.  2004,  34:  2223 

<A NAME="RF07105SS-9B">9b</A> Song Q.-B. Li X.-N. Shen T.-H. Yang S.-D. Qiang G.-R. Wu X.-L. Ma Y.-X. Synth. Commun.  2003,  33:  3935 

<A NAME="RF07105SS-10A">10a</A> Wnuk SF. Ro BO. Valdez CA. Lewandowska E. Valdez NX. Sacasa PR. Yin D. Zhang JS. Borchardt RT. De Clercq E. J. Med. Chem.  2002,  45:  2651 

<A NAME="RF07105SS-10B">10b</A> Smith AB. Brandt BM. Org. Lett.  2001,  3:  1685 

<A NAME="RF07105SS-11A">11a</A> Hassan J. Sévignon M. Gozzi C. Schulz E. Lemaire M. Chem. Rev.  2002,  102:  1359 

<A NAME="RF07105SS-11B">11b</A> Smith GB. Dezeny GC. Hughes DL. King AO. Verhoeven TR. J. Org. Chem.  1994,  59:  8151 

<A NAME="RF07105SS-11C">11c</A> Aliprantis AO. Canary JW. J. Am. Chem. Soc.  1994,  116:  6985 

<A NAME="RF07105SS-12">12</A> Graham PJ. Lindsey RV. Parshall GW. Peterson ML. Whitman GM. J. Am. Chem. Soc.  1957,  79:  3416 

<A NAME="RF07105SS-13A">13a</A> Hawkins RT. Lennarz WJ. Snyder HR. J. Am. Chem. Soc.  1960,  82:  3053 

<A NAME="RF07105SS-13B">13b</A> Feulner H. Linti G. Noth H. Chem. Ber.  1990,  123:  1841 

<A NAME="RF07105SS-13C">13c</A> Coulson DR. Inorg. Synth.  1972,  13:  121 

<A NAME="RF07105SS-14A">14a</A> Zhang G.-L. Synthesis  2005,  537 

<A NAME="RF07105SS-14B">14b</A> Deng Y.-J. Gong L.-Z. Mi A.-Q. Liu H. Jiang Y.-Z. Synthesis  2003,  337