Conversion of leucomycin-A sub(3) antibiotic into novel triazole analogues via regio- and diastereoselective S sub(N)1' substitution with allylic rearrangement and 1,3-dipolar cycloaddition of CuAAC type

In view of the complicated chemistry of josamycin's (leucomycin-A sub(3)) acetal functional groups, reduction of the aldehyde followed by nucleophilic substitution of josamycin's dienol system in the aglycone yielded novel products having an alkyne group attached at the C(13) carbon atom....

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Published inTetrahedron letters Vol. 57; no. 15; pp. 1661 - 1666
Main Authors Domagalska, Joanna, Pyta, Krystian, Przybylski, Piotr
Format Journal Article
LanguageEnglish
Published 13.04.2016
Subjects
Alkynes
Antibiotics
Bearing
Carbon
Conversion
Mathematical analysis
Tetrahedrons
Triazoles
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Summary:In view of the complicated chemistry of josamycin's (leucomycin-A sub(3)) acetal functional groups, reduction of the aldehyde followed by nucleophilic substitution of josamycin's dienol system in the aglycone yielded novel products having an alkyne group attached at the C(13) carbon atom. Detailed super(1)H- super(1)H NOESY and super(1)H- super(13)C HMBC investigations together with DFT calculations indicated the C(13S) configuration within the structures of alkyne-functionalized leucomycins. Analysis of the relationship between the rate of nucleophilic substitution and concentration revealed the unimolecular mechanism of the substitution with protonation of the leaving group as the rate determining step. Further conversion of the alkyne substituent on the aglycone using the CuAAC reaction provided access to novel heterocyclic leucomycin analogues bearing substituted 1,2,3-triazole rings.
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ISSN:0040-4039
DOI:10.1016/j.tetlet.2016.02.113