Reaction of 9-oxabicyclo[4.2.1]non-7-ene-1-ol with tetrazine: An unusually facile intramolecular rearrangement

Reaction of (1S*,7R*)-9-oxabicyclo[4.2.1]non-7-en-1-ol (5) with dimethyl 1,2,4,5-tetrazine-3,6-dicarboxylate (6) produced (2R*,4R*)-dimethyl 4-(7-oxooxepan-2-yl)-1,4-dihydropyridazine-3,6-dicarboxylate (11) in a one-pot reaction involving cycloaddition at ambient conditions. The structure of the rea...

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Bibliographic Details
Published in:Tetrahedron 2017-09, Vol.73 (36), p.5381-5388
Main Authors: Kaya, Afşin A., Salamci, Emine, Menzek, Abdullah, Erdem, Safiye S., Şahin, Ertan, Ecer, Kadriye
Format: Article
Language:English
Subjects:
1,4-Epoxide
Caprolactone
DFT
Diels Alder
Mechanism
Rearrangement
Retro-ene
Tetrazine
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Summary:Reaction of (1S*,7R*)-9-oxabicyclo[4.2.1]non-7-en-1-ol (5) with dimethyl 1,2,4,5-tetrazine-3,6-dicarboxylate (6) produced (2R*,4R*)-dimethyl 4-(7-oxooxepan-2-yl)-1,4-dihydropyridazine-3,6-dicarboxylate (11) in a one-pot reaction involving cycloaddition at ambient conditions. The structure of the rearrangement product 11 was determined by X-ray crystallographic analysis. Its formation was discussed based on experimental studies and density functional theory calculations. The driving force of this unusually facile reaction was the stability of the caprolactone product 11 and the extremely exorgenic loss of N2. Structural factors facilitating this rearrangement were also explored employing PCM//M06-2X/6-31G(d, p) calculations. [Display omitted]
ISSN:0040-4020
1464-5416
DOI:10.1016/j.tet.2017.07.040