A new catalyticroute has been developedforthe couplingof epoxidesand CO2affordingpolymer-izable six-memberedbicycliccarbonates.Cyclic epoxidesequippedwith aβ-positionedOH group can be trans-formedinto structurallydiversebicycliccyclic carbo-nates in good yields and with high selectivity.Key to thechemo-selectivityis the differencebetweenthe reactivityofsyn- andanti-configuredepoxyalcohols,with thelatter leadingto six-memberedring carbonateformationin the presenceof a binaryAlIIIaminotriphenolatecomplex/DIPEAcatalyst.X-ray analysesshow that theconversionof thesyn-configuredsubstrateevolvesvia astandarddoubleinversionpathwayprovidinga five-memberedcarbonateproduct,whereastheanti-isomerallows for activationof the oxiraneunit of the substrateoppositeto the pendentalcohol.The potentialuse ofthese bicyclicproductsis shownin ring-opening poly-merizationofferingaccess to rigid polycarbonates with improved thermal resistance.

A Novel Catalytic Route to Polymerizable Bicyclic Cyclic Carbonate Monomers from Carbon Dioxide

Arianna Brandolese;
2022

Abstract

A new catalyticroute has been developedforthe couplingof epoxidesand CO2affordingpolymer-izable six-memberedbicycliccarbonates.Cyclic epoxidesequippedwith aβ-positionedOH group can be trans-formedinto structurallydiversebicycliccyclic carbo-nates in good yields and with high selectivity.Key to thechemo-selectivityis the differencebetweenthe reactivityofsyn- andanti-configuredepoxyalcohols,with thelatter leadingto six-memberedring carbonateformationin the presenceof a binaryAlIIIaminotriphenolatecomplex/DIPEAcatalyst.X-ray analysesshow that theconversionof thesyn-configuredsubstrateevolvesvia astandarddoubleinversionpathwayprovidinga five-memberedcarbonateproduct,whereastheanti-isomerallows for activationof the oxiraneunit of the substrateoppositeto the pendentalcohol.The potentialuse ofthese bicyclicproductsis shownin ring-opening poly-merizationofferingaccess to rigid polycarbonates with improved thermal resistance.
2022
Qiao, Chang; Shi, Wangyu; Brandolese, Arianna; Benet-Buchholz, Jordi; Escudero-Adán, Eduardoc.; Kleij, Arjan W.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11392/2491134
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