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    • 11. 发明授权
    • Asymmetric ring-closing metathesis reactions involving achiral and meso substrates
    • 涉及非手性和内消旋底物的不对称闭环复分解反应
    • US06346652B1
    • 2002-02-12
    • US09114692
    • 1998-07-13
    • Richard R. SchrockAmir H. Hoveyda
    • Richard R. SchrockAmir H. Hoveyda
    • C07C602
    • C07B53/00C07B57/00C07F7/1892C07F11/005Y02P20/582Y10S585/94
    • A composition and method for the catalytic conversion of a racemic mixture of dienes to a cyclic olefin by a ring-closing metathesis (RCM) reaction are disclosed. The composition, a transition metal complex with an M═C reaction site, contains a bidentate dialkoxide of at least 80% optical purity. Because the M═C reaction site is of a sufficient shape specificity, conferred in part by the dialkoxide of sufficient rigidity and a M═N—R1 site, reacting the composition with a mixture of two enantiomeric dienes results in an olefin metathesis product that has at least a 50% enantiomeric excess of one enantiomer in the mixture. A method is also provided for reacting a composition with a racemic diene mixture to generate a metathesis product that has an enantiomeric excess of at least 50%. Methods are also provided for catalytic enantioselective desymmetrization. One method involves an olefin metathesis reaction with a molecular substrate having a plane of symmetry to form a product free of a plane of symmetry. Another method provides a desymmetrization reaction to occur in the absence of solvent. A method for producing quaternary carbon centers through a desymmetrization reaction is also described.
    • 公开了通过闭环复分解(RCM)反应将二烯的外消旋混合物催化转化成环状烯烃的组合物和方法。 该组合物是具有M = C反应位点的过渡金属络合物,其含有至少80%光学纯度的二齿二烷氧基化物。 由于M = C反应位点具有足够的形状特异性,部分由二烷氧基赋予足够的刚性和M = N-R1位点,使组合物与两种对映异构体二烯的混合物反应,得到烯烃复分解产物,其具有 在混合物中至少50%对映异构体过量的一种对映异构体。 还提供了使组合物与外消旋二烯混合物反应以产生具有至少50%的对映异构体过量的复分解产物的方法。 还提供了催化对映选择性去对称化的方法。 一种方法涉及与具有对称平面的分子底物的烯烃复分解反应以形成不具有对称平面的产物。 另一种方法提供在不存在溶剂的情况下发生的不对称反应。 还描述了通过不对称反应生产季碳中心的方法。
    • 14. 发明授权
    • Dimerization of olefins using tantalum and niobium catalysts
    • 使用钽和铌催化剂对烯烃进行二聚
    • US4245131A
    • 1981-01-13
    • US54211
    • 1979-07-02
    • Richard R. Schrock
    • Richard R. Schrock
    • C07C2/34C07F9/00C07C2/26
    • C07F9/00C07C2/34C07C2531/22
    • Tantalum and niobium catalysts or catalyst precursors of the formula: ##STR1## wherein R is cyclopentadienyl, which can be substituted with methyl up to five positions, or neopentylidene, R.sup.1 is neopentyl or benzyl, n is 0 or 1, R.sup.2 is neopentylidene, benzylidene, tetramethylene, or 2,3-dimethyltetramethylene, A is halo or a moiety of the formula YR.sup.3 R.sup.4 R.sup.5 wherein Y is a group 5 element including N, P, As, Sb and Bi and R.sup.3, R.sup.4, R.sup.5 can be the same or different and are C.sub.1 -C.sub.4 alkyl, aralkyl such as naphthyl, neophyl, tolyl or xylyl, aryl such as benzyl or phenyl or bipyridyl and Z is tantalum or niobium. The compounds selectively dimerize 1-olefins to 1-butenes; m=1 or 2.
    • 钽和铌催化剂或下式的催化剂前体:其中R是环戊二烯基,其可以被甲基取代至五个位置,或新戊基,R1是新戊基或苄基,n是0或1,R2是新亚戊基,亚苄基 ,四亚甲基或2,3-二甲基四亚甲基,A是卤素或式YR 3 R 4 R 5的部分,其中Y是包括N,P,As,Sb和Bi的第5族元素,并且R 3,R 4,R 5可以相同或不同, 是C 1 -C 4烷基,芳烷基如萘基,烯丙基,甲苯基或二甲苯基,芳基如苄基或苯基或联吡啶基,Z是钽或铌。 该化合物选择性地将1-烯烃二聚成1-丁烯; m = 1或2。
    • 19. 发明申请
    • Olefin metathesis catalysts and related methods
    • 烯烃复分解催化剂及相关方法
    • US20080119678A1
    • 2008-05-22
    • US11603951
    • 2006-11-22
    • Adam S. HockRichard R. Schrock
    • Adam S. HockRichard R. Schrock
    • B01J31/00C07C2/00
    • B01J31/2295B01J31/122B01J31/1805B01J31/181B01J31/2234B01J31/2265B01J31/2291B01J2231/482B01J2231/54B01J2231/543B01J2531/64B01J2531/66C07C6/04C07C2531/22
    • The present invention provides methods for the synthesis of catalysts and precursors thereof. Methods of the invention may comprise combining a catalyst precursor and at least one ligand to generate a catalytically active species, often under mild conditions and in high yields. In some cases, a wide variety of catalysts may be synthesized from a single catalyst precursor. Methods of the invention may also include the preparation of catalysts which, under reaction conditions known in the art, may have been difficult or impossible to prepare and/or isolate due to, for example, steric crowding at the metal center. The present invention also provides catalyst compositions, and precursors thereof, which may be useful in various chemical reactions including olefin metathesis. In some cases, methods of the invention may reduce the number of synthetic and purification steps required to produce catalysts and/or other reaction products, as well as reducing time, cost, and waste production.
    • 本发明提供合成催化剂及其前体的方法。 本发明的方法可以包括将催化剂前体和至少一种配体结合以产生催化活性物质,通常在温和条件下和高产率下。 在一些情况下,可以从单一催化剂前体合成多种催化剂。 本发明的方法还可以包括催化剂的制备,其在本领域已知的反应条件下可能由于例如在金属中心的空间拥挤而难以或不可能制备和/或分离。 本发明还提供催化剂组合物及其前体,其可用于包括烯烃复分解的各种化学反应。 在一些情况下,本发明的方法可以减少制备催化剂和/或其它反应产物所需的合成和纯化步骤的数量,以及减少时间,成本和废物的产生。