Studies of the synthetic applications of element-organic compounds of 15th and 16th Groups. 97. Pentaorganylstiborane. 2. Reactions of pentaorganylstiboranes with acyl chlorides and ketones
synthesized from aldehydes or ketones and allylicacetates, using an electrochemical process catalyzed by iron complexes. We first studied the reactivity of allyl acetate, using N,N-dimethylformamide (DMF) or acetonitrile (AN) as solvent, FeBr(2) as catalyst, and Fe as the sacrificial anode. Then we tested the regioreactivity of crotyl acetate and other allylic derivatives.
The electroreduction of a catalytic amount of ZnBr2 in acetonitrile provided a active Zn*, able to catalyze the reductive coupling of allyl bromides and chlorides with carbonyl compounds with high regioselectivity. Substituted α-methylene γ-lactones were obtained from functionalized allyl derivatives.
Allylation of ketones has been efficiently performed using iron-complex catalysis and led to homoallylic alcohols in high yields. (c) 2006 Elsevier Ltd. All rights reserved.
Direct transformation of allylic and benzylic alcohols or their silylated derivatives into organolithium compounds
作者:Emma Alonso、David Guijarro、Miguel Yus
DOI:10.1016/0040-4020(95)00709-h
日期:1995.10
The reaction of allylic or benzylic alcohols 1 with n-butyllithium followed by treatment with lithium powder and a catalytic amount of DTBB (5 mol %) in THF at room temperature gives a solution of the corresponding alkyllithium reagent, which reacts in situ with different electrophiles to yield the expected products 2. Alternatively, the O-silylated derivatives of the same alcohols are lithiated under Barbier-type reaction conditions to afford the same reaction products with better yields.
BENKESER R. A.; SIKLOSI M. P.; MOZDZEN E. C., J. AMER. CHEM. SOC., 1978, 100 17 2134-2139