Highly Selective Addition Reaction Of Catalyzed Conjugated Diene

Conjugated olefins are a common and important structural unit in many drug molecules and natural products.Compared with ordinary olefins,conjugated olefins exhibit unique stability and addition characteristics due to their unique multi-π conjugated system.Therefore,the research on the participation of conjugated olefins has important significance in both theoretical research and industrial applications.In this paper,the reaction of several common conjugated olefin compounds,benzo fulvene,p-QMs and 1-benzene-1,3-butadiene,under the catalysis of chiral phosphine,Lewis acid and protonic acid were studied.The first part of this paper mainly studies the asymmetric [3+2] cycloaddition reaction of benzofurene with MBH carbonate.Under the catalysis of our developed chiral tertiary phosphine,The [3+2] cycloaddition product was obtained with high yield and high diastereoselectivity under mild conditions.This is the first asymmetric ring addition reaction of γ,δ position and MBH carbonate to the π-conjugated system acceptor by a nucleophilic catalyst.The reaction has excellent substrate suitability and mild reaction conditions.High yield,enantioselectivity and diastereoselectivity.It has potential application value in the synthetic development of spiro skeleton catalysts.In the second part of this paper,the addition reaction of p-QMs with phenylacetylene was achieved by copper catalysis or iron catalysis.This is the first report of the 1,6-Michael addition reaction of phenylacetylene C(sp)as a nucleophile and p-QMs.The 1,6-Michael addition reaction of phenylacetylene with p-QMs under copper catalysis gives an alkynyldiarylmethane derivative.Under iron catalysis,benzene acetylene,p-QMs and hydrohalic acid are reacted in three components to obtain a diarylmethane halogenated olefin product.The reaction has excellent substrate suitability,and under mild conditions,HF,HCl,HBr,and HI can obtain the target product in a moderate to excellent yield.In summary,two diarylmethane compounds were synthesized by copper-catalyzed or iron-catalyzed reaction of p-QMs with phenylacetylene,and the possible mechanism was proposed.In the third part,the selective para-functionalization reaction of phenol is achieved by protonic acid catalyzed conjugated olefin.1-Benzene-1,3-butadiene undergoes selective para-carbon-hydrogen bond functionalization with phenol under the catalysis of inexpensive protonic acid TfOH,which has mild reaction conditions,good substrate suitability and Moderate to good yield.The resulting phenol para-functionalized products have potential applications in natural products and drug molecules.