Enantioselective one-carbon expansion of aromatic rings by simultaneous formation and chromoselective irradiation of a transient coloured enolate
Rakesh K. Saunthwal, James Mortimer, Andrew J. Orr‐Ewing, Jonathan Clayden
Abstract
-benzylbenzamides. The cascade of reactions leading to the products entails enantioselective benzylic deprotonation with a chiral lithium amide, dearomatizing cyclization of the resulting configurationally defined organolithium to give an extended amide enolate, and photochemically induced formal [1,7]-sigmatropic rearrangement and 6π-electrocyclic ring-opening - the latter all evidently being stereospecific - to deliver enantioenriched cycloheptatrienes with embedded benzylic stereocentres.
Topics & Concepts
ChromophoreEnantioselective synthesisAromaticityChemistryRing (chemistry)AmideIrradiationPhotochemistryTransient (computer programming)Aromatic amino acidsOrganic chemistryCatalysisMoleculePhysicsComputer scienceNuclear physicsEnzymeOperating systemAsymmetric Synthesis and CatalysisRadical Photochemical ReactionsSynthetic Organic Chemistry Methods