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TitleDiels–alder reactions of alkyl 2H-azirine-3-carboxylates with furans
Author(s)Alves, M. José
Azóia, Nuno G.
Bickley, Jamie F.
Fortes, A. Gil
Gilchrist, Thomas L.
Mendonça, Ricardo
Issue date2001
PublisherRoyal Society of Chemistry
JournalJournal of the Chemical Society-Perkin Transactions 1
CitationAlves, M. J., Azoia, N. G., Bickley, J. F., Fortes, A. G., Gilchrist, T. L., & Mendonça, R. (2001). Diels–Alder reactions of alkyl 2H-azirine-3-carboxylates with furans. Journal of the Chemical Society, Perkin Transactions 1. Royal Society of Chemistry (RSC).
Abstract(s)Methyl 2-(2,6-dichlorophenyl)-2H-azirine-3-carboxylate 1 and furan give the aziridine 2 by a Diels–Alder cycloaddition reaction. The hydrolysis of compound 2 leads to a dihydrofuranol 11 by cleavage of a C–N bond. X-Ray crystal structures of compounds 2 and 11 have been determined. Compound 2 reacts with alcohols in a similar way to give 2-alkoxy-2,5-dihydrofurans as mixtures of cis and trans isomers. The structures of these compounds have been determined from an X-ray crystal structure of one of the methyl ethers, the trans isomer 13. The reaction of the azirine 1 with 1,3-diphenylisobenzofuran leads to the formation of two isomeric 1 : 1 adducts that have been identified as the products of endo and exo cycloaddition, 3 and 4. The endo isomer 3 is converted into the exo isomer 4 by heat. Similar Diels–Alder reactions have been carried out between furans and benzyl 2H-azirine-3-carboxylate 6. Hydrolysis of the adduct 7 formed with furan again produces a dihydrofuranol 25 as the major product together with three minor products, two of which are 1-azabicyclo[4.1.0]hept-3-ene-2,5-diols 27 and 28 that result from C–O bond cleavage. Protection of the mixture of alcohols with TBS triflate gives the bis(TBS) ether 31 of the trans-1-azabicyclo[4.1.0]hept-3-ene-2,5-diol as the major product, showing that this ring system can be produced from the dihydrofuranol 25. The bis(TBS) ether 30 of the cis-2,5-diol is a minor product and its structure has been established by independent synthesis through a Diels–Alder reaction between the azirine 6 and 1,4-bis(tert-butyldimethylsilyloxy)butadiene 32.
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