公开(公告)号：US20140194604A1

公开(公告)日：2014-07-10

申请号：US14149924

申请日：2014-01-08

申请人： CALIFORNIA INSTITUTE OF TECHNOLOGY

发明人： Bill MORANDI ,  Robert H. GRUBBS ,  Zachary K. WICKENS

IPC分类号： C07D209/48 ,  C07C45/28 ,  C07C67/29 ,  C07C245/24 ,  C07C303/30

CPC分类号： C07D209/48 ,  C07B41/06 ,  C07C45/28 ,  C07C51/373 ,  C07C67/29 ,  C07C67/313 ,  C07C201/12 ,  C07C231/12 ,  C07C247/04 ,  C07C303/30 ,  C07C303/40 ,  C07C2601/14 ,  C07C49/255 ,  C07C49/175 ,  C07C49/173 ,  C07C235/74 ,  C07C311/16 ,  C07C205/57 ,  C07C309/73 ,  C07C49/403 ,  C07C49/04 ,  C07C49/84 ,  C07C49/784 ,  C07C69/14 ,  C07C69/84 ,  C07C69/78 ,  C07C59/76 ,  C07C69/716

摘要： The present invention is directed to methods for oxidizing internal olefins to ketones. In various embodiments, each method comprising contacting an organic substrate, having an initial internal olefin, with a mixture of (a) a biscationic palladium salt; and (b) an oxidizing agent; dissolved or dispersed in a solvent system to form a reaction mixture, said solvent system comprising at least one C2-6 carbon nitrile and optionally at least one secondary alkyl amide, said method conducted under conditions sufficient to convert at least 50 mol % of the initial internal olefin to a ketone, said ketone positioned on a carbon of the initial internal olefin. The transformation occurs at room temperature and shows wide substrate scope. Applications to the oxidation of seed oil derivatives and a bioactive natural product are described.

摘要翻译： 本发明涉及将内烯烃氧化成酮的方法。 在各种实施方案中，每种方法包括使具有初始内烯烃的有机基质与（a）双阳离子钯盐的混合物接触; 和（b）氧化剂; 溶解或分散在溶剂体系中以形成反应混合物，所述溶剂体系包含至少一种C 2-6碳腈和任选的至少一种仲烷基酰胺，所述方法在足以将至少50mol％的初始 内部烯烃与酮反应，所述酮位于初始内烯烃的碳上。 转化在室温下发生，显示出宽的底物范围。 描述了种子油衍生物和生物活性天然产物的氧化应用。

公开(公告)号：US20140051817A1

公开(公告)日：2014-02-20

申请号：US14066962

申请日：2013-10-30

申请人： CALIFORNIA INSTITUTE OF TECHNOLOGY

发明人： Robert H. GRUBBS ,  PETER SCHWAB ,  SONBINH T. NGUYEN

IPC分类号： C08F4/80

CPC分类号： C08F4/80 ,  B01J31/18 ,  B01J31/2265 ,  B01J31/24 ,  B01J31/2404 ,  B01J2231/14 ,  B01J2231/543 ,  B01J2531/821 ,  B01J2531/825 ,  C07F15/002 ,  C07F15/0046 ,  C08F32/00 ,  C08G61/08

摘要： Ruthenium and osmium carbene compounds that are stable in the presence of a variety of functional groups and can be used to catalyze olefin metathesis reactions on unstrained cyclic and acyclic olefins are disclosed-of the formula where M is Os or Ru; R1 is hydrogen; R is selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, and substituted or unsubstituted aryl; X and X1 are independently selected from any anionic ligand; and L and L1 are independently selected from any neutral electron donor. The ruthenium and osmium carbene compounds of the present invention may be synthesized using diazo compounds, by neutral electron donor ligand exchange, by cross metathesis, using acetylene, using cumulated olefins, and in a one-pot method using diazo compounds and neutral electron donors. The ruthenium and osmium carbene compounds may be used to catalyze olefin metathesis reactions.

摘要翻译： 在各种官能团存在下稳定并可用于催化烯烃复分解反应的钌和锇卡宾化合物在下列公式中公开：其中M为Os或Ru; R1是氢; R选自氢，取代或未取代的烷基和取代或未取代的芳基; X和X 1独立地选自任何阴离子配体; L和L 1独立地选自任何中性给电子体。 本发明的钌和锇卡宾化合物可以使用重氮化合物，通过中性电子给体配体交换，通过交叉复分解，使用乙炔，使用累积的烯烃，以及使用重氮化合物和中性电子给体的一锅法合成。 钌和锇卡宾化合物可用于催化烯烃复分解反应。