公开(公告)号：US09096519B2

公开(公告)日：2015-08-04

申请号：US14149924

申请日：2014-01-08

Applicant: California Institute of Technology

Inventor： Bill Morandi ,  Robert H. Grubbs ,  Zachary K. Wickens ,  Michael M. Lerch

IPC: C07C303/30 ,  C07C303/40 ,  C07D209/48 ,  C07C45/28 ,  C07C67/29 ,  C07C201/12 ,  C07C231/12 ,  C07C247/04 ,  C07C67/313 ,  C07C51/373 ,  C07B41/06

CPC classification number: 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

Abstract: 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.

Abstract translation: 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。