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

Y. Becker; A. Eisenstadt; Y. Shvo

doi:10.1016/S0040-4020(01)97145-5

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

Y. Becker, A. Eisenstadt, Y. Shvo

Tel Aviv University

Research output: Contribution to journal › Article › peer-review

27 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 S_N2′-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 language	English
Pages (from-to)	839-847
Number of pages	9
Journal	Tetrahedron
Volume	30
Issue number	7
DOIs	https://doi.org/10.1016/S0040-4020(01)97145-5
State	Published - 1974
Externally published	Yes

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.

Funding

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.

Funders	Funder number
Eshkol Fund
National council for Researcha ndD

Access to Document

10.1016/S0040-4020(01)97145-5

Cite this

@article{fb967c707c784f6e8a04090cc4ebdf01,

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

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.",

author = "Y. Becker and A. Eisenstadt and Y. Shvo",

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.",

year = "1974",

doi = "10.1016/S0040-4020(01)97145-5",

language = "אנגלית",

volume = "30",

pages = "839--847",

journal = "Tetrahedron",

issn = "0040-4020",

publisher = "Elsevier Ltd.",

number = "7",

}

TY - JOUR

T1 - Reaction of transition metal carbonyls with heterocyclic systems-II. Diironnonarcarbonyl and 1,2-oxazines

AU - Becker, Y.

AU - Eisenstadt, A.

AU - Shvo, Y.

N1 - 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.

PY - 1974

Y1 - 1974

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=0141969114&partnerID=8YFLogxK

U2 - 10.1016/S0040-4020(01)97145-5

DO - 10.1016/S0040-4020(01)97145-5

M3 - ???researchoutput.researchoutputtypes.contributiontojournal.article???

AN - SCOPUS:0141969114

SN - 0040-4020

VL - 30

SP - 839

EP - 847

JO - Tetrahedron

JF - Tetrahedron

IS - 7

ER -

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

Abstract

Bibliographical note

Funding

Access to Document

Other files and links

Fingerprint

Cite this