Diastereoselective Transformations of Enol Esters Derived from Acetylenes and Chiral Carboxylic Acids

Abstract

Markovnikov-type enol esters are synthesized selectively from N-protected amino acids by ruthenium-mediated coupling with the appropriate acetylenes. Subsequent hydrogenation of the enol esters over Adams’ catalyst gives the corresponding saturated products in moderate to good diastereoselectivities. The enol esters undergo reaction with m-chloroperoxybenzoic acid to yield α-acyl­oxy ketones, as the products of rearrangement, instead of the expected epoxides.

enol esters - diastereoselectivity - hydrogenation - epoxidation - ruthenium

References

<A NAME="RT25711SS-1A">1a</A> Wexler A. Balchunis RJ. Swenton JS. J. Chem. Soc., Chem. Commun.  1975,  601 

<A NAME="RT25711SS-1B">1b</A> Jung ME. Hudspeth JP. J. Am. Chem. Soc.  1978,  100:  4309 

<A NAME="RT25711SS-1C">1c</A> Pirrung MC. Lee YR. Tetrahedron Lett.  1994,  35:  6231 

<A NAME="RT25711SS-2">2</A> Motherwell WB. Roberts LR. J. Chem. Soc., Chem. Commun.  1992,  1582 

<A NAME="RT25711SS-3">3</A> Reetz MT. Goossen LJ. Meiswinkel A. Paetzold J. Jensen JF. Org. Lett.  2003,  5:  3099 

For example, see:

<A NAME="RT25711SS-4A">4a</A> Boaz NW. Tetrahedron Lett.  1998,  39:  5505 

<A NAME="RT25711SS-4B">4b</A> Tang W. Liu D. Zhang X. Org. Lett.  2003,  5:  205 

<A NAME="RT25711SS-4C">4c</A> Wu S. Wang W. Tang W. Lin M. Zhang X. Org. Lett.  2002,  4:  4495 

<A NAME="RT25711SS-4D">4d</A> Szőri K. Szöllősi G. Felföldi K. Bartók M. React. Kinet. Catal. Lett.  2005,  84:  151 

<A NAME="RT25711SS-5">5</A> Isambert N. Cruz M. Arévalo J. Gómez E. Lavilla R. Org. Lett.  2007,  9:  4199 

<A NAME="RT25711SS-6">6</A> Jeong JU. Tao B. Sagasser I. Henniges H. Sharpless KB. J. Am. Chem. Soc.  1998,  120:  6844 

<A NAME="RT25711SS-7">7</A> Feng X. Shi Y. J. Org. Chem.  2002,  67:  2831 

<A NAME="RT25711SS-8">8</A> Draper AL. Heilman WJ. Schaepfer WE. Shine HJ. Shoolery JN. J. Org. Chem.  1962,  27:  2727 

<A NAME="RT25711SS-9A">9a</A> Larock RC. Oertle K. Beatty KM. J. Am. Chem. Soc.  1980,  102:  1966 

<A NAME="RT25711SS-9B">9b</A> Bach RD. Woodard RA. Anderson TJ. Glick MD. J. Org. Chem.  1982,  47:  3707 

<A NAME="RT25711SS-10">10</A> Nakagawa H. Okimoto Y. Sakaguchi S. Ishii Y. Tetrahedron Lett.  2003,  44:  103 

<A NAME="RT25711SS-11">11</A> Hua R. Tian X. J. Org. Chem.  2004,  69:  5782 

<A NAME="RT25711SS-12">12</A> Rotem M. Shvo Y. Organometallics  1983,  2:  1689 

<A NAME="RT25711SS-13A">13a</A> Mitsudo T. Hori Y. Watanabe Y. J. Org. Chem.  1985,  50:  1566 

<A NAME="RT25711SS-13B">13b</A> Ruppin C. Dixneuf PH. Tetrahedron Lett.  1988,  29:  5365 

<A NAME="RT25711SS-14">14</A> Le Gendre P. Comte V. Michelot A. Moise C. Inorg. Chim. Acta  2003,  350:  289 

<A NAME="RT25711SS-15">15</A> Goossen LJ. Paetzold J. Koley D. Chem. Commun.  2003,  706 

<A NAME="RT25711SS-16">16</A>

The detailed structural parameters have been deposited with the Cambridge Crystallographic Data Centre (CCDC 805409).

<A NAME="RT25711SS-17">17</A>

The detailed structural parameters have been deposited with the Cambridge Crystallographic Data Centre (CCDC 805410).

<A NAME="RT25711SS-18">18</A>

MestReNova software, v. 6.2.1-7569, 2010, Mestrelab Research SL, Santiago de Compostela, Spain.

<A NAME="RT25711SS-19">19</A> Sheldrick GM. SHELXS97. Program for solving crystal structures   University of Gottingen; Germany: 1997. 

<A NAME="RT25711SS-20">20</A> Sheldrick GM. SHELXL97. Program for crystal structure refinement   University of Gottingen; Germany: 1997. 

<A NAME="RT25711SS-21">21</A> Tanaka K. Honke S. Urbańczyk-Lipkowska Z. Toda F. Eur. J. Org. Chem.  2000,  3171