Synthesis of functionalized and unfunctionalized olefins via...

C - Chemistry – Metallurgy – 07 – C

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C07C 67/02 (2006.01) C07B 37/00 (2006.01) C07C 45/67 (2006.01) C07C 45/69 (2006.01) C07C 45/72 (2006.01) C07C 61/35 (2006.01) C07C 67/293 (2006.01) C07C 67/343 (2006.01) C07C 205/06 (2006.01) C07C 231/12 (2006.01) C07C 233/09 (2006.01) C07C 259/06 (2006.01) C07C 315/04 (2006.01) C07C 317/14 (2006.01) C07D 263/04 (2006.01) C07D 263/24 (2006.01) C07D 303/04 (2006.01) C07D 303/22 (2006.01) C07D 309/12 (2006.01) C07D 309/16 (2006.01) C07D 309/18 (2006.01) C07D 315/00 (2006.01) C07D 317/12 (2006.01) C07D 319/12

Patent

CA 2413852

The invention is directed to the cross-metathesis and ring-closing metathesis reactions between geminal disubstituted olefins and terminal olefins, wherein the reaction employs a Ruthenium or Osmium metal carbene complex. Specifically, the invention relates to the synthesis of .alpha.-functionalized or unfunctionalized olefins via intermolecular cross-metathesis and intramolecular ring-closing metathesis using a ruthenium alkylidene complex. The catalysts preferably used in the invention are of general formula (I) or (II), wherein: M is ruthenium or osmium; X and X1 are each independently an anionic ligand; L is a neutral electron donor ligand; and, R, R1, R6, R7, R8, and R9 are each independently hydrogen or a substituent selected from the group consisting of C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, aryl, C1-C20 carboxylate, C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20 alkynyloxy, aryloxy, C2- C20 alkoxycarbonyl, C1-C20 alkylthio, C1-C20 alkylsulfonyl and C1-C20 alkylsulfinyl.

L'invention concerne des réactions de métathèse croisée et de métathèse à fermeture de cycle entre des oléfines disubstituées géminales et des oléfines terminales, ces réactions utilisant un complexe carbène-ruthénium ou carbène-osmium. Plus particulièrement, l'invention concerne la synthèse d'oléfines .alpha.-fonctionnalisées ou non fonctionnalisées par métathèse croisée et par métathèse à fermeture de cycle intramoléculaire au moyen d'un complexe d'alkylidène de ruthénium. Les catalyseurs préférés de l'invention sont représentés par la formule (I) ou (II), où M est ruthénium ou osmium, X et X?1¿ sont chacun indépendamment un ligand anionique, L est un ligand donneur d'électrons neutre, et R, R?1¿, R?6¿, R?7¿, R?8¿, et R?9¿ sont chacun indépendamment hydrogène ou un substituant choisi dans le groupe constitué par alkyle C¿1?-C¿20?, alcényle C¿2?-C¿20?, alcynyle C¿2?-C¿20?, aryle, carboxylate C¿1?-C¿20?, alcoxy C¿1?-C¿20?, alcényloxy C¿2?-C¿20?, alcynyloxy C¿2?-C¿20?, aryloxy, alcoxycarbonyle C¿2?-C¿20?, alkylthio C¿1?-C¿20?, alkylsulfonyle C¿1?-C¿20? et alkylsulfinyle C¿1?-C¿20?.

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