Radical Reaction Initiated and Stereocontrolled by Zinc Chloride
摘要:
The reaction of allyltributyltin with methyl 2-[N-((4S)-4-(1-methylethyl)-2-oxazolidinone-3-carbamoyl)amino]-2-bromoacetate (5a) was accelerated at -50 degrees C in the presence of AIBN and stopped in the presence of galvinoxyl, indicating that the reaction proceeds through a radical mechanism. The reaction was accelerated dramatically at -78 degrees C in the presence of ZnCl2 . OEt2, and the ZnCl2-mediated reaction was stopped in the presence of galvinoxyl. In the presence of 2 equiv ZnCl2 . OEt2, the reaction afforded methyl (2R)-2-[N-((4S)-4-(1-methylethyl)-2-oxazolidinone-3- carbamoyl)amino]4-pentenoate {6a(R)} with high diastereoselectivity (93:7). Taken together, ZnCl2 . OEt2 works as a radical initiator as well as chelating agent.
Reactions of diphenylcarbene with alkenes, alkynes, and alkenynes
作者:William J. Baron、Michael E. Henrick、Maitland. Jones
DOI:10.1021/ja00800a022
日期:1973.9
Regioselectivity and rearrangement upon addition of nucleophiles to dieneiron complexes
作者:M. F. Semmelhack、Hanh T. M. Le
DOI:10.1021/ja00321a049
日期:1984.5
Nucleophilic addition to coordinated polyenes: a novel method for the liberation of the trimethylenemethane ligand involving CC bond formation
作者:William A. Donaldson、M.Azad Hossain
DOI:10.1016/s0040-4039(00)74664-8
日期:1992.7
Reaction of (trimethylenemethane)Fe(CO)3 with carbon nucleophiles, followed by protonation yields the corresponding methallylated nucleophile in good yield. Products which incorporate carbonyl ligands are also observed.
MAYR H.; POCK R., CHEM. BER., 119,(1986) N 8, 2473-2496