The Investigation Of Fe(?)-Catalyzed Hydrobenzylation And Hydroalkynylation Of Alkenes & Addition/Arrangement/Cyclization Reaction Of Ynamides With Carboxylic Acids

Olefins and alkynes are basic organic chemicals,the efficient transformation of olefins and alkynes is interesting and important.We have developed methods of Fe(?)-catalyzed hydrofunctionalization of olefins.With Fe(acac)3 as catalyst and phenylsilane as reducing agent,the non-activated olefin undergoes hydrogen atom transfer reaction(HAT)to obtain alkyl radicals,which added to radical receptors like para-Quinone Methides(p-QMs)and alkynyl bromide to achieve the hydrobenzylation and hydroalkylation of olefins,various phenols and alkynes could be formed,and these methods are applied to functionalization of natural products;Control reactions are conducted to elucidate plausible mechanism.Alkynamides are a class of electron-rich alkynes with dual properties of nucleophilic and electrophilic.The addition reaction of carboxylic acid with alkyne amide gives an acyloxyenamide intermediate.We studied the homo-Passerini reaction of the acyloxyenamide intermediate and aldehyde under Lewis-acid to obtain ?-ester amide compound;Meanwhile,the acyloxyenamide intermediate could undergo sulfonyl migration rearrangement reaction to obtain a plurality of linear and heterocyclic compounds upon heating;On the other hand,the acyloxyenamide intermediate from alkynyl carboxylic acid could convert to ?-pyrone derivative under simple conditions,which could engaged in the intramolecular and intermolecular Diels-Alder reactions for accessing various heterocycles.The corresponding reaction mechanism was proved by deuteration experiments and control experiments.The main contents of this paper include four aspects:1.Under the Fe(acac)3/phenylsilane system,the olefin is converted into alkyl radical(HAT),which realizes the first 1,6-radical addition of p-QMs,completes the hydrobenzylation reaction of olefin,and converts p-QMs to phenol derivatives.2.Alkyl radicals formed by olefins in Fe(acac)3/phenylsilane system react with addition-elimination of alkynyl bromide to realize Csp-Csp3 coupling,complete alkynylation of olefins and obtain various forms of alkynes.3.Addition reaction between alkynamide and carboxylic acid resulted in the homo-Passerines reaction of acyloxyenamide intermediates with aldehydes catalyzed by BF3-OEt2,resulting in the formation of beta easterly amides and phenolphthalein derivatives.The sulfonyl 1,3-migration reaction of alkene ether intermediates occurred under heating conditions,accompanied by Mumm rearrangement,and the resulting products could undergo further transformation under the action of alkali.4.Acyloxyenamide intermediates formed by acetylenic acid and acetylenamide were cyclized under direct heating or silver trifluoromethanesulfonate catalysis to obtain alpha-pyranone derivatives.Diels-Alder cyclization of alpha-pyranone was further carried out intramolecular and intermolecular to obtain indolin derivatives and aniline derivatives.