Synthesis and reactions of 2-epoxyethylenepyridine 1-oxide with nitrogen, oxygen, and sulfur nucleophiles

Reaction of 2(3,4)‐pyridinecarboxaldehydes (5) with ethylidenetriphenylphosphorane afford a mixture of stereoisomers Z‐(6) and E‐1‐[2(3,4)‐pyridinyl]‐1‐propenes (7). m‐Chloroperbenzoic acid oxidation of 6 and 7 yields a 60:40 mixture of Z‐(8) and E‐1‐[1‐oxido‐2(3,4)‐pyridinyl]‐2‐methyloxiranes (9). The regiospecific reaction of Z‐isomers 8a‐c with cyclic amines as piperidine give rise to threo‐1‐hydroxy‐1‐[1‐oxido‐2(3,4)‐pyridinyl]‐2‐(1‐piperidino)propanes (10) while the E‐isomer 9a yields erythro‐11. On tho other hand, the E‐isomers 9b and 9c having 1‐oxido‐3(4)‐pyridinyl substituents afford erythro‐12 resulting from attack by piperidine at C‐1 of the oxirane. Reductive deoxygenation using 10% palladium on charcoal and hydrogen gas effectively removed the N‐oxide substituent from the threo‐10 and erythro‐11 β‐aminoalcohols. Dilute solution ir spectroscopy indicated the existance of strong intramolecular hydrogen bonding in the β‐aminoalcohols 10 and 11. The assignment of relative configuration of diastereoisomers 10 and 11 was based on the magnitude of the vicinal coupling constant J where J threo is greater than J erythro.

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Synthesis and reactions of heterocyclic methyl 2‐propenoates and 2,3‐epoxypropanoates with nucleophiles

Agarwal

Knaus

1985

Journal of Heterocyclic Chem

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Reaction of 2‐(3‐,4‐)pyridinecarboxaldehydes 5 with carbomethoxymethylene triphenylphosphorane afforded predominantly E‐methyl‐3‐(pyridinyl)‐2‐propenoates 7. Oxidation of 7a‐c with m‐chloroperbenzoic acid gave methyl E‐3‐(1‐oxidopyridinyl)‐2‐propenoates 8a‐c in high yield. The Darzen's reaction of 5a‐c with methyl bromoacetate yielded a mixture of stereoisomers cis‐9a‐c and methyl trans‐3‐(pyridinyl)‐2,3‐epoxy‐propanoates 10a‐c in a ratio of 2:1. Oxidation of cis‐9a‐c and trans‐10a‐c afforded the corresponding cis‐11a‐c and methyl trans‐3‐(1‐oxidopyridinyl)‐2,3‐epoxypropanoates 12a‐c in good yield. The reaction of 11a and 12a with cyclic amines as piperidine gave the respective threo‐13 and methyl erythro‐2‐(1‐piperidino)‐3‐hydroxy‐3‐(1‐oxido‐2‐pyridino)propanoate 14. The sodium borohydride reduction of the N‐alkoxylcarbonyl pyridinium salts of 9c and 10c afforded the corresponding N‐alkoxycarbonyl‐1,2‐dihydropyridyl derivatives 15 and 16. A number of selected compounds (7a‐c, 9a‐c, 10a, 10c, 11a‐c and 12a, 12c) were found to be inactive in the P388 Lymphocytic screen. Compounds 9‐12 did not react with the model nucleophile ethanethiol in phosphate buffer at 37°.

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Synthesis and reactions of 2-epoxyethylenepyridine 1-oxide with nitrogen, oxygen, and sulfur nucleophiles

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ChemInform Abstract: SYNTHESIS AND REACTIONS OF 2‐EPOXYETHYLPYRIDINE 1‐OXIDE WITH NITROGEN, OXYGEN, AND SULFUR NUCLEOPHILES

ChemInform Abstract: SYNTHESIS AND REACTIONS OF 2‐EPOXYETHYLPYRIDINE 1‐OXIDE WITH NITROGEN, OXYGEN, AND SULFUR NUCLEOPHILES

Synthesis and reactions of 1‐[1‐oxido‐2‐(3,4)‐pyridinyl]‐2‐methyloxiranes with nitrogen nucleophiles

Synthesis and reactions of heterocyclic methyl 2‐propenoates and 2,3‐epoxypropanoates with nucleophiles

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