Tandem Isomerization/Claisen Rearrangement of Diallyl- and Allylhomoallyl­ethers: In Situ Conversion of Grubbs’ Catalyst to a Ru-H Species

Abstract

Diallyl- and allylhomoallylethers do not undergo the expected ring closing metathesis reaction if ethyl vinyl ether is added to the reaction mixture. Instead, upon heating, a selective isomerization of the substrates to allyl vinyl ethers is induced. These then ­undergo a Claisen rearrangement to produce pent-4-enals.

catalysis - rearrangements - ruthenium - tandem reactions

References

Reviews on olefin metathesis:

<A NAME="RG10504ST-1A">1a</A> Armstrong SK. J. Chem. Soc., Perkin Trans. 1  1998,  371 

<A NAME="RG10504ST-1B">1b</A> Fürstner A. Top. Organomet. Chem.  1998,  1:  37 

<A NAME="RG10504ST-1C">1c</A> Fürstner A. Angew. Chem. Int. Ed.  2000,  39:  3013 

<A NAME="RG10504ST-1D">1d</A> Connon SJ. Blechert S. Angew. Chem. Int. Ed.  2003,  42:  1900 

Selected examples:

<A NAME="RG10504ST-2A">2a</A> Crimmins MT. Choy AL. J. Org. Chem.  1997,  62:  7548 

<A NAME="RG10504ST-2B">2b</A> Leeuwenburgh MA. Overkleeft HS. van der Marel GA. van Boom JH. Synlett  1997,  1263 

<A NAME="RG10504ST-2C">2c</A> Maier ME. Bugl M. Synlett  1998,  1390 

<A NAME="RG10504ST-2D">2d</A> Schmidt B. Wildemann H. Eur. J. Org. Chem.  2000,  3145 

<A NAME="RG10504ST-2E">2e</A> Izzo I. Del Gaudio P. Della Monica C. Squitieri M. De Riccardis F. Heterocycles  2003,  60:  2057 

<A NAME="RG10504ST-2F">2f</A> Heck M.-P. Baylon C. Nolan SP. Mioskowski C. Org. Lett.  2001,  3:  1989 

<A NAME="RG10504ST-3">3</A> Review: Elliott MC. J. Chem. Soc., Perkin Trans. 1  2002,  2301 ; and previous reviews cited therein

<A NAME="RG10504ST-4">4</A> Schwab P. Grubbs RH. Ziller JW. J. Am. Chem. Soc.  1996,  118:  100 

<A NAME="RG10504ST-5">5</A> Alcaide B. Almendros P. Chem.-Eur. J.  2003,  9:  1259 

<A NAME="RG10504ST-6A">6a</A> Maynard HD. Grubbs RH. Tetrahedron Lett.  1999,  40:  4137 

<A NAME="RG10504ST-6B">6b</A> Bourgeois D. Pancrazi A. Ricard L. Prunet J. Angew. Chem. Int. Ed.  2000,  39:  725 

<A NAME="RG10504ST-6C">6c</A> Edwards SD. Lewis T. Taylor RJK. Tetrahedron Lett.  1999,  40:  4267 

<A NAME="RG10504ST-6D">6d</A> Fürstner A. Thiel OR. Ackermann L. Schanz H.-J. Nolan SP. J. Org. Chem.  2000,  65:  2204 

<A NAME="RG10504ST-6E">6e</A> Schmidt B. Wildemann H. J. Org. Chem.  2000,  65:  5817 

<A NAME="RG10504ST-6F">6f</A> Bourgeois D. Pancrazi A. Nolan SP. Prunet J. J. Organomet. Chem.  2002,  643-644:  247 

<A NAME="RG10504ST-7A">7a</A> Kinderman SS. van Maarseveen JH. Schoemaker HE. Hiemstra H. Rutjes FPJT. Org. Lett.  2001,  3:  2045 

<A NAME="RG10504ST-7B">7b</A> Cadot C. Dalko PI. Cossy J. Tetrahedron Lett.  2002,  43:  1839 

<A NAME="RG10504ST-7C">7c</A> Alcaide B. Almendros P. Alonso JM. Chem.-Eur. J.  2003,  9:  5793 

RCM/hydrogenation:

<A NAME="RG10504ST-8A">8a</A> Louie J. Bielawski CW. Grubbs RH. J. Am. Chem. Soc.  2001,  123:  11312 

<A NAME="RG10504ST-8B">8b</A> Borsting P. Nielsen P. Chem. Commun.  2002,  2140 

<A NAME="RG10504ST-8C">8c</A> Fürstner A. Leitner A. Angew. Chem. Int. Ed.  2003,  42:  308 

<A NAME="RG10504ST-8D">8d</A> Schmidt B. Pohler M. Org. Biomol. Chem.  2003,  1:  2512 

<A NAME="RG10504ST-8E">8e</A> RCM/isomerization: Sutton AE. Seigal BA. Finnegan DF. Snapper ML. J. Am. Chem. Soc.  2002,  124:  13390 

<A NAME="RG10504ST-8F">8f</A> Schmidt B. Eur. J. Org. Chem.  2003,  816 

<A NAME="RG10504ST-8G">8g</A> Schmidt B. Chem. Commun.  2004,  742 

<A NAME="RG10504ST-9A">9a</A> Arisawa M. Terada Y. Nakagawa M. Nishida A. Angew. Chem. Int. Ed.  2002,  41:  4732 

<A NAME="RG10504ST-9B">9b</A> Schmidt B. Pohler M. Costisella B. J. Org. Chem.  2004,  69:  1421 

Reviews:

<A NAME="RG10504ST-10A">10a</A> Spring DR. Org. Biomol. Chem.  2003,  1:  3867 

<A NAME="RG10504ST-10B">10b</A> Burke MD. Schreiber SL. Angew. Chem. Int. Ed.  2004,  43:  46 

Examples for tandem isomerization/Claisen rearrangement:

<A NAME="RG10504ST-11A">11a</A> Reuter JM. Salomon RG. J. Org. Chem.  1977,  42:  3360 

<A NAME="RG10504ST-11B">11b</A> Swenton JS. Bradin D. Gates BD. J. Org. Chem.  1991,  56:  6156 

<A NAME="RG10504ST-11C">11c</A> Iyer RS. Kobierski ME. Salomon RG. J. Org. Chem.  1994,  59:  6038 

<A NAME="RG10504ST-11D">11d</A> Mitchell TN. Gießelmann F. Synlett  1996,  475 

<A NAME="RG10504ST-11E">11e</A> Wille A. Tomm S. Frauenrath H. Synthesis  1998,  305 

<A NAME="RG10504ST-11F">11f</A> Higashino T. Sakaguchi S. Ishii Y. Org. Lett.  2000,  2:  4193 

<A NAME="RG10504ST-11G">11g</A> Le Nôtre J. Brissieux L. Sémeril D. Bruneau C. Dixneuf PH. Chem. Commun.  2002,  1772 

<A NAME="RG10504ST-11H">11h</A> Ben Ammar H. Le Nôtre J. Salem M. Kaddachi MT. Dixneuf PH. J. Organomet. Chem.  2002,  662:  63 

<A NAME="RG10504ST-11I">11i</A> Ben Ammar H. Le Nôtre J. Salem M. Kaddachi MT. Toupet L. Renaud J.-L. Bruneau C. Dixneuf PH. Eur. J. Inorg. Chem.  2003,  4055 

<A NAME="RG10504ST-11J">11j</A> Nelson SG. Bungard CJ. Wang K. J. Am. Chem. Soc.  2003,  125:  13000 

<A NAME="RG10504ST-12">12</A> For an example describing the use of pent-4-enals in target molecule synthesis, see: Sattelkau T. Hollmann C. Eilbracht P. Synlett  1996,  1221 

<A NAME="RG10504ST-13">13</A> Review: Schmidt B. Eur. J. Org. Chem.  2004,  1865 

<A NAME="RG10504ST-14A">14a</A> Louie J. Grubbs RH. Organometallics  2002,  21:  2153 

<A NAME="RG10504ST-14B">14b</A> Dinger MB. Mol JC. Organometallics  2003,  22:  1089 

Hydride-carbonyl complexes of ruthenium were originally obtained from RuCl₃·xH₂O, methanol and an appropriate phosphine ligand:

<A NAME="RG10504ST-15A">15a</A> Esteruelas MA. Werner H. J. Organomet. Chem.  1986,  303:  221 

<A NAME="RG10504ST-15B">15b</A> Esteruelas MA. Liu F. Onate E. Sola E. Zeier B. Organometallics  1997,  16:  2919 

<A NAME="RG10504ST-15C">15c</A> Yi CS. Lee DW. Organometallics  1999,  18:  5152 ; the chemistry of some other Ru-H complexes is discussed in ref. 13

<A NAME="RG10504ST-16">16</A> Yamamoto Y. Nakagai Y. Ohkoshi N. Itoh K. J. Am. Chem. Soc.  2001,  123:  6372