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A Rh(I)‐Catalyzed Cascade Cyclization of 1,5‐Bisallenes and Alkynes for the Formation of <i>cis‐</i>3,4‐Arylvinyl Pyrrolidines and Cyclopentanes

Jordi Vila, Roger Vinardell, Miquel Solà, Anna Pla‐Quintana, Anna Roglans

2021Advanced Synthesis & Catalysis14 citationsDOIOpen Access PDF

Abstract

Abstract The cascade cyclization reactions of 1,5‐bisallenes grant access to a great variety of products by precisely tuning the catalyst system and/or the reagents involved. Herein, we present our findings that 1,5‐bisallenes react with two molecules of dimethyl acetylenedicarboxylate to afford, in a completely diastereoselective manner, cis ‐3,4‐arylvinyl pyrrolidines and cyclopentanes. DFT calculations have been used to postulate a mechanism for the developed reaction which encompasses a [2+2+2] cycloaddition reaction of the two alkynes and the external double bond of one allene, followed by a cycloisomerization involving the internal double bond of the second allene. magnified image

Topics & Concepts

CyclopentanesChemistryAlleneCycloisomerizationDimethyl acetylenedicarboxylateCatalysisCycloadditionReagentDouble bondCascadeCascade reactionAlkyneTriple bondMedicinal chemistryCombinatorial chemistryStereochemistryOrganic chemistryChromatographyCatalytic Alkyne ReactionsCatalytic C–H Functionalization MethodsCyclopropane Reaction Mechanisms
A Rh(I)‐Catalyzed Cascade Cyclization of 1,5‐Bisallenes and Alkynes for the Formation of <i>cis‐</i>3,4‐Arylvinyl Pyrrolidines and Cyclopentanes | Litcius