公开(公告)号：EP1301458A1

公开(公告)日：2003-04-16

申请号：EP01950437.2

申请日：2001-06-25

Applicant: CALIFORNIA INSTITUTE OF TECHNOLOGY

Inventor： GRUBBS, Robert, H. ,  CHATTERJEE, Arnab, K. ,  MORGAN, John, P. ,  SCHOLL, Matthias ,  CHOI, Tae-Lim

IPC: C07C67/02 ,  C07C317/14 ,  C07C233/09 ,  C07C205/06 ,  C07C61/35 ,  C07D323/02 ,  C07D263/04 ,  C07D303/04 ,  C07D309/16 ,  C07D309/18 ,  C07F7/04 ,  C07F9/28 ,  C07F15/00

CPC classification number: C07D303/22 ,  C07B37/00 ,  C07C45/673 ,  C07C45/69 ,  C07C45/72 ,  C07C67/293 ,  C07C67/343 ,  C07C201/12 ,  C07C231/12 ,  C07C259/06 ,  C07C315/04 ,  C07D263/22 ,  C07D263/24 ,  C07D309/12 ,  C07D309/30 ,  C07D315/00 ,  C07D317/12 ,  C07D319/12 ,  C07D319/14 ,  C07D321/08 ,  C07D413/12 ,  C07C49/597 ,  C07C317/14 ,  C07C233/09 ,  C07C233/11 ,  C07C205/06 ,  C07C205/56

Abstract: 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 α-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, R?1, R6, R7, R8, and R9¿ are each independently hydrogen or a substituent selected from the group consisting of C¿1?-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.

公开(公告)号：EP1301458B1

公开(公告)日：2015-09-09

申请号：EP01950437.2

申请日：2001-06-25

Applicant: CALIFORNIA INSTITUTE OF TECHNOLOGY

Inventor： GRUBBS, Robert, H. ,  CHATTERJEE, Arnab, K. ,  MORGAN, John, P. ,  SCHOLL, Matthias ,  CHOI, Tae-Lim

IPC: C07C317/14 ,  C07C233/09 ,  C07C205/06 ,  C07C61/35 ,  C07D323/02 ,  C07D263/04 ,  C07D303/04 ,  C07D309/18 ,  C07F7/04 ,  C07B37/00 ,  C07C45/67 ,  C07C45/69 ,  C07C45/72 ,  C07C67/293 ,  C07C67/343 ,  C07C231/12 ,  C07C259/06 ,  C07C315/04 ,  C07D303/22 ,  C07C309/12 ,  C07D315/00 ,  C07D317/12 ,  C07D319/12 ,  C07D321/08 ,  C07D263/22 ,  C07D309/30 ,  C07D319/14

CPC classification number: C07D303/22 ,  C07B37/00 ,  C07C45/673 ,  C07C45/69 ,  C07C45/72 ,  C07C67/293 ,  C07C67/343 ,  C07C201/12 ,  C07C231/12 ,  C07C259/06 ,  C07C315/04 ,  C07D263/22 ,  C07D263/24 ,  C07D309/12 ,  C07D309/30 ,  C07D315/00 ,  C07D317/12 ,  C07D319/12 ,  C07D319/14 ,  C07D321/08 ,  C07D413/12 ,  C07C49/597 ,  C07C317/14 ,  C07C233/09 ,  C07C233/11 ,  C07C205/06 ,  C07C205/56

公开(公告)号：EP1373170A1

公开(公告)日：2004-01-02

申请号：EP02731215.6

申请日：2002-04-01

Applicant: California Institute of Technology

Inventor： GRUBBS, Robert, H. ,  CHATTERJEE, Arnab, K. ,  CHOI, Tae-Lim ,  GOLDBERG, Steven, D. ,  LOVE, Jennifer, A. ,  MORGAN, John, P. ,  SANDERS, Daniel, P. ,  SCHOLL, Matthias ,  TOSTE, F., Dean ,  TRNKA, Tina, M.

IPC: C07C6/02 ,  C07C6/04 ,  C07C6/06

CPC classification number: C07F9/40 ,  C07C6/04 ,  C07C17/275 ,  C07C29/40 ,  C07C29/46 ,  C07C41/14 ,  C07C45/69 ,  C07C67/293 ,  C07C67/297 ,  C07C67/343 ,  C07C67/475 ,  C07C201/12 ,  C07C319/20 ,  C07C2531/22 ,  C07C2601/14 ,  C07C2601/16 ,  C07C2603/74 ,  C07D263/14 ,  C07D317/12 ,  C07D317/20 ,  C07D317/24 ,  C07F7/1892 ,  C07F9/4015 ,  C07F15/0046 ,  C07C25/13 ,  C07C47/21 ,  C07C69/007 ,  C07C69/78 ,  C07C69/732 ,  C07C69/56 ,  C07C321/14 ,  C07C69/16 ,  C07C69/533 ,  C07C69/145 ,  C07C69/157 ,  C07C69/18 ,  C07C205/06 ,  C07C33/483

Abstract: The invention pertains to the use of Group 8 transition metal carbene complexes as catalysts for olefin cross-metathesis reactions. In particular, ruthenium and osmium alkylidene complexes substituted with an N-heterocyclic carbene ligand are used to catalyze cross-metathesis reactions to provide a variety of substituted and functionalized olefins, including phosphonate-substituted olefins, directly halogenated olefins, 1,1,2-trisubstituted olefins, and quaternary allylic olefins. The invention further provides a method for creating functional diversity using the aforementioned complexes to catalyze cross-metathesis reactions of a first olefinic reactant, which mayor may not be substituted with a functional group, with each of a plurality of different olefinic reactants, which may or may not be substituted with functional groups, to give a plurality of structurally distinct olefinic products. The methodology of the invention is also useful in facilitating the stereoselective synthesis of 1,2-disubstituted olefins in the cis configuration.

公开(公告)号：EP1180108B1

公开(公告)日：2003-08-27

申请号：EP00937665.8

申请日：2000-05-22

Applicant: CALIFORNIA INSTITUTE OF TECHNOLOGY

Inventor： GRUBBS, Robert, H. ,  SCHOLL, Matthias

IPC: C07F15/00

CPC classification number: C07F15/002 ,  C07F15/0046

Abstract: The present invention relates to novel metathesis catalysts with an imidazolidine-based ligand and to methods for making and using the same. The inventive catalysts are of formula (I) wherein : M is ruthemium or osmium; X and X are each independently an anionic ligand; L is a neutral electron donor ligand; and, R, R , R , R , R and R 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 alkylthiol, aryl thiol, C1-C20 alkylsulfonyl and C1-C20 alkylsulfinyl, the substituent optionally substituted with one or more moieties selected from the group consisting of C1-C10 alkyl, C1-C10 alkoxy, aryl, and a functional group selected from the group consisting of hydroxyl, thiol thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, and halogen. The inclusion of an imidazolidine ligand to the previously described ruthenium or osmium catalysts has been found to dramatically improve the properties of theses complexes. The inventive catalysts maintains the functional group tolerance of previously described ruthenium complexes while having enhanced metathesis activity that compares favorably to prior art tungsten and molybdenum systems.

公开(公告)号：EP1180108A2

公开(公告)日：2002-02-20

申请号：EP00937665.8

申请日：2000-05-22

Applicant: CALIFORNIA INSTITUTE OF TECHNOLOGY

Inventor： GRUBBS, Robert, H. ,  SCHOLL, Matthias

IPC: C07F15/00

CPC classification number: C07F15/002 ,  C07F15/0046

Abstract: The present invention relates to novel metathesis catalysts with an imidazolidine-based ligand and to methods for making and using the same. The inventive catalysts are of formula (I) wherein : M is ruthemium or osmium; X and X are each independently an anionic ligand; L is a neutral electron donor ligand; and, R, R , R , R , R and R 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 alkylthiol, aryl thiol, C1-C20 alkylsulfonyl and C1-C20 alkylsulfinyl, the substituent optionally substituted with one or more moieties selected from the group consisting of C1-C10 alkyl, C1-C10 alkoxy, aryl, and a functional group selected from the group consisting of hydroxyl, thiol thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, and halogen. The inclusion of an imidazolidine ligand to the previously described ruthenium or osmium catalysts has been found to dramatically improve the properties of theses complexes. The inventive catalysts maintains the functional group tolerance of previously described ruthenium complexes while having enhanced metathesis activity that compares favorably to prior art tungsten and molybdenum systems.