How To Enhance the Efficiency of Breslow Intermediates for SET Catalysis - CNRS - Centre national de la recherche scientifique
Article Dans Une Revue Journal of Organic Chemistry Année : 2023

How To Enhance the Efficiency of Breslow Intermediates for SET Catalysis

Résumé

Oxidativecarbeneorganocatalysis,whichproceedsviasingleelectrontransfer(SET) pathways, hasbeen limitedby themoderately reducingpropertiesof deprotonatedBreslow intermediatesBI−sderivedfromthiazol-2-ylidene1and1,2,4-triazolylidene2.Usingcomputational methods,weassesstheredoxpotentialsofBI−sbasedontendifferenttypesofknownstablecarbenes andreportourfindingsconcerningthekeyparametersinfluencingthestepsofthecatalyticcycle. FromthecalculatedvaluesofthefirstoxidationpotentialofBI−sderivedfromcarbenes1to10,it appearsthat,apartfromthediamidocarbene7,alltheothersaremorereducingthanthiazol-2-ylidene 1andthe1,2,4-triazolylidene2.WeobservedthatwhilethereducingpowerofBI−ssignificantly decreaseswithincreasingsolventpolarity,theredoxpotentialoftheoxidantcanincreaseatagreater rate,thusfacilitatingthereaction.Thecation,associatedwiththebase,alsoplaysanimportantrole whenanonpolarsolventisused;largeandweaklycoordinatingcationssuchasCs+arebeneficial.The radical−radicalcouplingstepisprobablythemostchallengingstepduetobothelectronicandsteric constraints.Basedonourresults,wepredictthatmesoioniccarbene3andabnormalNHC4arethe mostpromisingcandidatesforoxidativecarbeneorganocatalysis.

Domaines

Chimie
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Dates et versions

hal-04285911 , version 1 (14-11-2023)

Identifiants

Citer

Florian F Mulks, Mohand Melaimi, Xiaoyu Yan, Mu-Hyun Baik, Guy Bertrand. How To Enhance the Efficiency of Breslow Intermediates for SET Catalysis. Journal of Organic Chemistry, 2023, 88 (4), pp.2535-2542. ⟨10.1021/acs.joc.2c02978⟩. ⟨hal-04285911⟩

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