127229-68-9Relevant academic research and scientific papers
Stereoselective synthesis of α-phenylchalcogeno-α,β-unsaturated esters
Silveira, Claudio C.,Braga, Antonio L.,Guerra, Robson B.
, p. 3395 - 3397 (2002)
Ethyl α-phenylchalcogeno α,β-unsaturated esters were prepared in a stereoselective manner by the reaction of ethyl propiolates with organocuprates, followed by the reaction with the appropriate electrophilic organosulfur, organoselenium or organotellurium source.
Synthesis and Reactions of α-Chloro-β,γ-unsaturated Esters. 1
Mathew, Jacob,Alink, Ben
, p. 3880 - 3886 (2007/10/02)
Four new α-chloro-β,γ-unsaturated esters were prepared in good yield by the reaction of hypochlorous acid with substituted ethyl 2-butenoates.Reaction of these substituted allylic chlorides with several nucleophiles has been investigated.Thiophenol in the presence of aqueous sodium hydroxide react with ethyl 2-chloro-3-methyl-3-butenoate (2) to give 6, whereas ethyl 2-chloro-2,3-dimethyl-3-butenoate (1) is unreactive.Tertiary allylic chlorides 1, 3 and 4 react with secondary amines to give exclusive abnormal SN2 reaction products.With benzylamine abnormal SN2 substitution is followed by cyclization to give 1-benzyl-3-pyrrolin-2-ones.While ethyl lithioacetate reacts with 1 to give acylation product 18, sodium diphenylmethide in liquid ammonia undergoes alkylation on the tertiary carbon possibly by an electron-transfer reaction pathway.Lithio-1,3-dithiane reacts with 1 to give 2,3-dimethyl-6,10-dithiaspirodec-2-en-1-one (20) via a two-step process, viz., acylation followed by anovel variation of the intramolecular abnormal SN2 reaction.Raney nickel desulfurization of 20 gave 2,3-dimethyl-2-cyclopenten-1-one.Synthetic and mechanistic implications of these results are discussed.
