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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1995 (1995), S. 667-671 
    ISSN: 0947-3440
    Keywords: 1,2-Oxazines, bis(trimethylsilyl)amino-substituted ; Hydrogenolysis ; Deprotonation ; Alkylation ; Deuteration ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1,2-Oxazine 1 was converted into an unusual condensation product 5 by treatment with tetra-n-butylammonium fluoride. The hydrogenolysis of 1 with Pd/C as catalyst provided the expected primary amine 9, whereas the same reaction with the ethoxycarbonyl-substituted 1,2-oxazine 2 as starting material gave the 4-methylproline derivative 10 after N-protection. Deprotonation at C-4 of 1 required rather harsh conditions but cleanly afforded the corresponding lithiated intermediate 11. Treatment of 11 with electrophiles provided the C-4-substituted derivatives 12-16 in good to moderate yield, but generally with very high diastereoselectivity. The overall substitution process preferentially occurs with retention of configuration which is explained by assuming ion pair structure B for intermediate 11.
    Additional Material: 4 Tab.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0009-2940
    Keywords: 1,2-Oxazines, lithiated ; Deprotonation ; Alkylation ; Deuteration ; Regioselectivity ; Calculations, MNDO ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 5,6-Dihydro-5-methylene-4H-1,2-oxazine 1 is smoothly converted by n-butyllithium into 1-Li which reacts with electrophiles such as D2O, carbonyl compounds, dimethyl sulfide, or an azo diester to give the γ-adducts 4a-4f. On the other hand, alkylation of 1-Li occurs exclusively at C-4 of the heterocycle and provides the α-adducts 3g and 3h. These reactions require the activation of 1-Li by tetramethylethylenediamine. Treatment with allyl bromide and methyl acrylate affords mixtures of regioisomers 3 and 4. 1,2-Oxazine 5 with a conjugated C = C bond is less acidic than 1 but is also converted into 1-Li, whilst compound 6, lacking the 6-methoxy group, is not deprotonated under standard conditions. The dianion of 1,2-oxazine 7 is generated by employing an excess of n-butyllithium. This dianion displays a similar regiochemical behavior as 1-Li. Deuterium is exclusively incorporated into the γ-position to give product 8, while methylation occurs at C-4 to produce 9. 1,2-Oxazine 3g with an additional 4-methyl group can also be metalated and affords γ-adducts 10 and 11 upon reaction with D2O or acetone. Treatment with methyl iodide gives a 3:1 mixture of regioisomers 12 and 13. Deuteration of 1,2-oxazines 14 and 16 bearing a 3-CF3 or 3-CO2Et substituent requires more severe deprotonation conditions to provide the γ-adducts 15 and 17 in moderate yields. MNDO calculations of neutral 1,2-oxazines, the corresponding carbanions, and the lithium compounds allow an insight into the structure and charge distribution of these species, and also an estimation of the relative acidities. The regioselectivity of reactions of 1-Li is discussed on the basis of these semiempirical calculations and comparison with related ambident nucleophiles.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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