Reaction of transition metal carbonyls with heterocyclic systems-II. Diironnonarcarbonyl and 1,2-oxazines

Y. Becker, A. Eisenstadt, Y. Shvo

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26 Scopus citations

Abstract

The reactivity of the {A figure is presented} bond towards diironnonacarbonyl was investigated. 3,6-Dihydro and tetrahydro-1,2-oxazines were used as model compounds. Reduction of the {A figure is presented} bond predominates in presence of water, while under anydrous conditions a CO insertion into the {A figure is presented} bond of tetrahydro-1,2-oxazine takes place. The 3,6-dihydro-1,2-oxazine in the presence of Fe2(CO)9 and water, yield π-allyl-Fe-σ-lactones. Carbon dioxide and aniline are also formed in this reaction. The amino alcohol 7 is an intermediate in this and analogous reactions. The lactone 3 under Al2O3 catalysis reacts with primary amines to yield the corresponding lactams. Mechanistic investigation of this reaction points towards a SN2′-like mechanism inasmuch as the attack of the base occurs on the terminal carbon of the π-allyl system. The lactam 4 could be readily converted into the complex π-crotonylideneaniline iron tricarbonyl for which an intramolecular 1,4-H shift was demonstrated by a labeling experiment with deuterium.

Original languageEnglish
Pages (from-to)839-847
Number of pages9
JournalTetrahedron
Volume30
Issue number7
DOIs
StatePublished - 1974
Externally publishedYes

Bibliographical note

Funding Information:
Acknowledgements-One of us (Y.B.) thanks the National council for Researcha ndD evelopmentfo r Scholarship from the Eshkol Fund. The authorsa re gratefult o Prof. A. Mandelbaumo f the Technion. Haifa for mass spectrald eterminationsW. e also thankM rs. R. Weininger for NMR determinations.

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