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    IMIDAZOLIDINE-BASED METAL CARBENE METATHESIS CATALYSTS
    23.
    发明申请
    IMIDAZOLIDINE-BASED METAL CARBENE METATHESIS CATALYSTS 审中-公开
    基于咪唑烷的金属碳元素催化剂

    公开(公告)号：US20150038724A1

    公开(公告)日：2015-02-05

    申请号：US14461180

    申请日：2014-08-15

    申请人： CALIFORNIA INSTITUTE OF TECHNOLOGY

    发明人： Robert H. GRUBBS ,  Matthias SCHOLL

    IPC分类号： C07F15/00

    CPC分类号： C07F15/0046 ,  B01J31/2273 ,  B01J31/2278 ,  B01J31/2295 ,  B01J2231/543 ,  B01J2531/821 ,  B01J2531/825 ,  C08G61/08

    摘要： 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 the formula 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 alkylthiol, aryl thiol, C1-C20 alkylsulfonyl and C2-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 these 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.

    摘要翻译： 本发明涉及具有咪唑烷类配体的新型复分解催化剂及其制备和使用方法。 本发明的催化剂具有下式：其中：M是钌或锇; X和X1各自独立地为阴离子配体; L是中性电子给体配体; 并且，R 1，R 2，R 6，R 7，R 8和R 9各自独立地为氢或选自C 1 -C 20烷基，C 2 -C 20烯基，C 2 -C 20炔基，芳基，C 1 -C 20羧酸酯，C 1 -C 20烷氧基，C 2 -C 20链烯氧基，C 2 -C 20炔氧基，芳氧基，C 2 -C 20烷氧基羰基，C 1 -C 20烷基硫醇，芳基硫醇，C 1 -C 20烷基磺酰基和C 2 -C 20烷基亚磺酰基，任选被一个或多个选自 由C 1 -C 10烷基，C 1 -C 10烷氧基，芳基和选自羟基，硫醇，硫醚，酮，醛，酯，醚，胺，亚胺，酰胺，硝基，羧酸的官能团组成的组 ，二硫化物，碳酸酯，异氰酸酯，碳二亚胺，碳烷氧基，氨基甲酸酯和卤素。 已经发现将咪唑烷配体包含在前述的钌或锇催化剂中可显着地改善这些络合物的性质。 本发明的催化剂保持了先前描述的钌络合物的官能团耐受性，同时具有与现有技术的钨和钼体系相比有利的增强的复分解活性。

    HIGHLY EFFICIENT SYNTHESIS OF Z-MACROCYCLES USING STEREORETENTIVE, RUTHENIUM-BASED METATHESIS CATALYSTS
    26.
    发明申请
    HIGHLY EFFICIENT SYNTHESIS OF Z-MACROCYCLES USING STEREORETENTIVE, RUTHENIUM-BASED METATHESIS CATALYSTS 有权

    公开(公告)号：US20210355099A1

    公开(公告)日：2021-11-18

    申请号：US17336756

    申请日：2021-06-02

    申请人： CALIFORNIA INSTITUTE OF TECHNOLOGY

    发明人： Tonia S. AHMED ,  Robert H. GRUBBS

    IPC分类号： C07D313/00 ,  B01J31/22

    摘要： A highly efficient, Z-selective ring-closing metathesis system for the formation of macrocycles using a stereoretentive, ruthenium-based catalyst supported by a dithiolate ligand is reported. This catalyst is demonstrated to be remarkably active as observed in initiation experiments showing complete catalyst initiation at −20° C. within 10 min. Using easily accessible diene starting materials bearing a Z-olefin moiety, macrocyclization reactions generated products with significantly higher Z-selectivity in appreciably shorter reaction times, in higher yield, and with much lower catalyst loadings than in previously reported systems. Macrocyclic lactones ranging in size from twelve-membered to seventeen-membered rings are synthesized in moderate to high yields (68-79% yield) with excellent Z-selectivity (95%-99% Z).

    Anti-Microbial Coating Materials
    27.
    发明申请
    Anti-Microbial Coating Materials 审中-公开

    公开(公告)号：US20180362714A1

    公开(公告)日：2018-12-20

    申请号：US15985966

    申请日：2018-05-22

    申请人： California Institute of Technology

    发明人： Robert H. GRUBBS ,  Choon Woo LEE

    IPC分类号： C08G73/02 ,  C09D179/02

    摘要： The disclosure provides methods and materials suitable for preparing coating layers on substrates. The coatings comprise quaternary amine groups and therefore impart anti-bacterial properties to the substrate. In one embodiment, for example, there is provided a quaternary amine-containing polymeric coating comprising propylene and ethylene repeat units.

    ORGANIC SYNTHESIS APPLICATIONS OF NON-AQUEOUS FLUORIDE SALT SOLUTIONS
    30.
    发明申请
    ORGANIC SYNTHESIS APPLICATIONS OF NON-AQUEOUS FLUORIDE SALT SOLUTIONS 审中-公开
    非水性氟化物盐溶液的有机合成应用

    公开(公告)号：US20170057908A1

    公开(公告)日：2017-03-02

    申请号：US15229026

    申请日：2016-08-04

    申请人： CALIFORNIA INSTITUTE OF TECHNOLOGY ,  THE REGENTS OF THE UNIVERSITY OF CALIFORNIA

    发明人： Simon C. JONES ,  Victoria K. DAVIS ,  Christopher M. BATES ,  Nebojsa MOMCILOVIC ,  Brett M. SAVOIE ,  Michael A. WEBB ,  Thomas F. MILLER, III ,  Robert H. GRUBBS ,  Jennifer M. MURPHY

    IPC分类号： C07C209/68

    CPC分类号： H01M10/0568 ,  C07C209/68 ,  H01M10/0525 ,  H01M10/054 ,  H01M10/0569 ,  H01M2300/0025

    摘要： Processes and reaction mixtures including non-aqueous solvent mixtures are presented. Non-aqueous solvent mixtures including fluoride salt and non-aqueous solvent combinations are provided that possess high fluoride ion concentrations useful for a range of applications, including organic synthesis. Further non-aqueous solvent mixtures are provided including a salt possessing a non-fluoride anion and a non-aqueous solvent that, when contacted with aqueous fluoride-containing reagents, extract fluoride ions to form non-aqueous fluoride-ion solutions possessing high fluoride-ion concentrations. The salts include an organic cation that does not possess a carbon in the β-position or does not possess a carbon in the β-position having a bound hydrogen. This salt structure facilitates its ability to be made anhydrous without decomposition. Example anhydrous fluoride salts include (2,2-dimethylpropyl)trimethylammonium fluoride and bis(2,2-dimethylpropyl)dimethylammonium fluoride. The combination of these fluoride salts with at least one fluorine-containing non-aqueous solvent (e.g., bis(2,2,2-trifluoroethyl)ether; (BTFE)) promotes solubility of the salt within the non-aqueous solvents.

    摘要翻译： 提出了包括非水溶剂混合物的方法和反应混合物。 提供包括氟化物盐和非水溶剂组合的非水溶剂混合物，其具有用于一系列应用的高氟离子浓度，包括有机合成。 提供了另外的非水溶剂混合物，包括具有非氟化物阴离子的盐和非水溶剂，当与含氟化物的试剂接触时，提取氟离子以形成具有高氟化物浓度的非氟化物离子溶液， 离子浓度。 所述盐包括在β-位上不具有碳或在具有结合氢的β位上不具有碳的有机阳离子。 该盐结构有助于其无分解的能力。 例如无水氟化物盐包括（2,2-二甲基丙基）三甲基氟化铵和二（2,2-二甲基丙基）二甲基氟化铵。 这些氟化物盐与至少一种含氟非水溶剂（例如双（2,2,2-三氟乙基）醚;（BTFE））的组合促进盐在非水溶剂中的溶解度。