A Convenient Route to Trifluoromethyl-Substituted Cyclopropane Derivatives

Abstract

A range of alkenes have been converted in a single step into the corresponding trifluoromethyl-substituted cyclopropanes by treatment with 2-diazo-l,l,l-trifluoroethane over metal catalysts. Application of the Gaspar-Roth procedure allowed the preparation of target compounds on a multi-gram scale. The practical utility of this reaction has been demonstrated by the synthesis of both diastereoisomers of the non-natural amino acid trifluoronorcoronamic acid in two steps.

fluorine - alkenes - amino acids - catalysts - diazo compounds

References

<A NAME="RZ28307SS-1A">1a</A> Faust R. Angew. Chem. Int. Ed.  2001,  40:  2251 

<A NAME="RZ28307SS-1B">1b</A> Donaldson WA. Tetrahedron  2001,  57:  8589 

<A NAME="RZ28307SS-1C">1c</A> Wessjohann LA. Brandt W. Thiemann T. Chem. Rev.  2003,  103:  1625 

<A NAME="RZ28307SS-2A">2a</A> Fluorine-Containing Amino Acids Synthesis and Properties   Kukhar VP. Soloshonok VA. John Wiley & Sons; New York: 1994. 

<A NAME="RZ28307SS-2B">2b</A> Wang R. Ksebati MB. Corbett TH. Kern ER. Drach JC. Zemlicka J. J. Med. Chem.  2001,  44:  4019 

<A NAME="RZ28307SS-2C">2c</A> Ruzza P. Siligardi G. Donella-Deana A. Calderan A. Hussain R. Rubini C. Cesaro L. Osler A. Guiotto A. Pinna LA. Borin G. J. Pept. Sci.  2006,  12:  462 

<A NAME="RZ28307SS-3A">3a</A> Pustovit YM. Ogojko PI. Nazaretian VP. Faryateva LB. J. Fluorine Chem.  1994,  69:  225 

<A NAME="RZ28307SS-3B">3b</A> Hell Z. Finta Z. Dmowski W. Faigl F. Pustovit YM. Töke L. Harmat V. J. Fluorine Chem.  2000,  104:  297 

<A NAME="RZ28307SS-4A">4a</A> Wang Y. Zhao X. Li Y. Lu L. Tetrahedron Lett.  2004,  45:  7775 

<A NAME="RZ28307SS-4B">4b</A> Jiang B. Zhang F. Xiong WA. Chem. Commun.  2003,  536 

<A NAME="RZ28307SS-5A">5a</A> Katagiri T. Irie M. Uneyama K. Tetrahedron: Asymmetry  1999,  10:  2583 

<A NAME="RZ28307SS-5B">5b</A> Katagiri T. Yamaji S. Handa M. Irie M. Uneyama K. Chem. Commun.  2001,  2054 

<A NAME="RZ28307SS-6">6</A> Lin P. Jiang J. Tetrahedron  2000,  56:  3635 ; and references therein

<A NAME="RZ28307SS-7A">7a</A> Atherton JH. Fields R. J. Chem. Soc. C  1967,  1450 

<A NAME="RZ28307SS-7B">7b</A> Atherton JH. Fields R. J. Chem. Soc. C  1968,  1507 

<A NAME="RZ28307SS-8A">8a</A> Adams J. Spero DM. Tetrahedron  1991,  47:  1765 

<A NAME="RZ28307SS-8B">8b</A> Wang Y. Zhu S. Zhu G. Huang Q. Tetrahedron  2001,  57:  7337 

<A NAME="RZ28307SS-8C">8c</A> Jiang B. Zhang X. Luo Z. Org. Lett.  2002,  4:  2453 

<A NAME="RZ28307SS-8D">8d</A> Müller P. Grass S. Shahi SP. Bernardinelli G. Tetrahedron  2004,  60:  4755 

<A NAME="RZ28307SS-8E">8e</A> Ghanem A. Lacrampe F. Aboul-Enein H. Schurig V. Monatsh. Chem.  2005,  136:  1205 

<A NAME="RZ28307SS-8F">8f</A> Denton JR. Sukumaran D. Davies HML. Org. Lett.  2007,  9:  2625 

<A NAME="RZ28307SS-9">9</A> Le Maux P. Juillard S. Simonneaux G. Synthesis  2006,  10:  1701 

<A NAME="RZ28307SS-10A">10a</A> Fujimoto Y. Irreverre F. Karle JM. Karle IL. Witkop B. J. Am. Chem. Soc.  1971,  93:  3471 

<A NAME="RZ28307SS-10B">10b</A> Doering WE. Roth WR. Tetrahedron  1963,  19:  715 ; and references therein

<A NAME="RZ28307SS-11">11</A>

Notably, Simonneaux and co-workers observed the stereoselective formation of only the trans-isomer 3a, while performing the trifluoromethyl-cyclopropanation of 3 over chiral metalloporphyrins (reference 9).

<A NAME="RZ28307SS-12A">12a</A> Salomon RG. Kochi JK. J. Am. Chem. Soc.  1973,  95:  3300 

<A NAME="RZ28307SS-12B">12b</A> Salomon RG. Salomon MF. Heyne TR. J. Org. Chem.  1975,  40:  756 

<A NAME="RZ28307SS-13">13</A> Mitchell RE. Phytochemistry  1985,  7:  1485 

<A NAME="RZ28307SS-14A">14a</A> Kolar AJ. Olsen RK. Synthesis  1977,  457 

<A NAME="RZ28307SS-14B">14b</A> Wieland T. Ohnacker G. Ziegler W. Chem. Ber.  1957,  90:  194 

<A NAME="RZ28307SS-15">15</A> Katagiri T. Irie M. Uneyama K. Org. Lett.  2000,  2:  2423