21711-85-3Relevant academic research and scientific papers
Employing Arynes for the Generation of Aryl Anion Equivalents and Subsequent Reaction with Aldehydes
Gaykar, Rahul N.,Bhunia, Anup,Biju, Akkattu T.
, p. 11333 - 11340 (2018/07/21)
Arynes are highly reactive intermediates, which are utilized for the electrophilic arylation of various X-H bonds (X = O, N, S etc.). Herein, a new synthetic strategy is demonstrated, where arynes are converted into aryl anion equivalents by treatment with phosphines and a base. The addition of phosphines to arynes form the phosphonium salts, which in the presence of a carbonate base generates the aryl anion equivalent. Subsequent addition of the aryl anions with aldehydes afforded the secondary alcohols.
Base-Catalyzed Stereospecific Isomerization of Electron-Deficient Allylic Alcohols and Ethers through Ion-Pairing
Martinez-Erro, Samuel,Sanz-Marco, Amparo,Bermejo Gómez, Antonio,Vázquez-Romero, Ana,Ahlquist, M?rten S. G.,Martín-Matute, Belén
, p. 13408 - 13414 (2016/10/22)
A mild base-catalyzed strategy for the isomerization of allylic alcohols and allylic ethers has been developed. Experimental and computational investigations indicate that transition metal catalysts are not required when basic additives are present. As in the case of using transition metals under basic conditions, the isomerization catalyzed solely by base also follows a stereospecific pathway. The reaction is initiated by a rate-limiting deprotonation. Formation of an intimate ion pair between an allylic anion and the conjugate acid of the base results in efficient transfer of chirality. Through this mechanism, stereochemical information contained in the allylic alcohols is transferred to the ketone products. The stereospecific isomerization is also applicable for the first time to allylic ethers, yielding synthetically valuable enantioenriched (up to 97% ee) enol ethers.
Enantioselective Synthesis of Succinic Acids and γ-Lactones via Palladium Catalysed Allylic Substitution Reactions
Dawson, Graham J.,Williams, Jonathan M. J.,Coote, Steven J.
, p. 2535 - 2546 (2007/10/03)
The palladium catalyzed reaction between non-symmetrical allyl acetates and sodiodimethylmalonate proceeds in high yields and enantioselectivities (up to 99percent ee) using a diphenylphosphinoaryl oxazoline ligand.The so-formed substitution products are transformed into enantiomerically enriched succinic acids and also into enantiomerically enriched γ-lactones.
THE-PALLADIUM-CATALYSED REDUCTIVE ADDITION OF ARYL IODIDES TO PROPARGYL ALCOHOLS: A ROUTE TO γ,γ-DIARYL ALLYLIC ALCOHOLS
Arcadi, A.,Cacchi, S.,Marinelli, F.
, p. 5121 - 5132 (2007/10/02)
The reaction of aryl iodides with ethynyl and arylethynyl, dialkyl carbinols in the presence of the tri- or dialkylammonium formate-palladium reagent provides a convenient route to γ,γ-diarylallylic alcohols.In the presence of arylethynyl, alkylcarbinols a lack of regioselectivity was observed and mixtures of β,γ-, γ,γ-diarylallylic alcohols, and α,β-unsaturated ketones were obtained.
