Use of the Intramolecular Heck Reaction for Forming Congested Quaternary Carbon Stereocenters. Stereocontrolled Total Synthesis of (±)-Gelsemine
作者:Andrew Madin、Christopher J. O'Donnell、Taeboem Oh、David W. Old、Larry E. Overman、Matthew J. Sharp
DOI:10.1021/ja055711h
日期:2005.12.1
elaborate the hydropyran ring of gelsemine from the endo-oriented nitrile substituent of pentacyclic Heck product 18 were unsuccessful. Important steps in the ultimately successful route to (+/-)-gelsemine (1) are as follows: (a) intramolecular Heck reaction of tricyclic beta-methoxy alpha,beta-unsaturated 2-iodoanilide 68 in the presence of silver phosphate to form pentacyclic product 69 having the
Intermolecular, Markovnikov Hydroamination of Vinylarenes with Alkylamines
作者:Masaru Utsunomiya、John F. Hartwig
DOI:10.1021/ja0375535
日期:2003.11.1
occurred through an eta3-arylethyl palladium complex. The reactions of this complex with alkylamines generated product in combination with regenerating free vinylarene, Pd(0), and ammonium salt. Thus, one hurdle to developing hydroamination of vinylarenes with palladium complexes is the faster elimination of free vinylarene from the eta3-arylethyl complex than addition to form the C-N bond. The feasibility