Syntheses and properties of 5-substituted [n](2,4)pyridinophanes, model compounds of NAD(P)

Tadayoshi Oikawa, Nobuhiro Kanomata, Masaru Tada

    Research output: Contribution to journalArticle

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    Abstract

    [n](2,4)Pyridinophane derivatives 5-8 having an ester or an amide group at the 5-position were synthesized by aza-Wittig reactions between β-substituted vinyliminophosphoranes and cyclic α,β-unsaturated ketones. [β-(Methoxycarbonyl)vinyl]- (1), [β-(N,N-tetramethylenecarbamoyl)vinyl]-(2), [β-(N-benzylcarbamoyl)vinyl]- (3), and (β-carbamoylvinyl)iminophosphorane (4) were synthesized from the corresponding vinyl azides and triphenylphosphine. The heptamethylene chains of 5-(methoxycarbonyl)[7](2,4)pyridinophane (5), 5-(N,N-tetramethylenecarbamoyl)[7](2,4)pyridinophane (6), and 5-(N-benzylcarbamoyl)[7](2,4)pyridinophane (7) flipped with ΔG = 11.2 (Tc = 10.3°C), 10.8 (Tc = 0.2°C), and 10.5 kcal/mol (Tc = -5.2°C), respectively. At lower temperatures, the three conformations of the heptamethylene bridge were frozen. Methylpyridinium iodides 10 (n = 7, 6, and 5) derived from 6 were reduced more easily [E1/2* (half height potential) = -1.65 V (n = 7); -1.63 V (n = 6); -1.29 V va Ag/AgCl (n = 5)] than the reference compound, 2,4-diethyl-5-(N,N-tetramethylenecarbamoyl)pyridinium ion (11) [E1/2* = -1.82 V vs Ag/AgCl]. The reduced species dimerized quickly.

    Original languageEnglish
    Pages (from-to)2046-2051
    Number of pages6
    JournalJournal of Organic Chemistry
    Volume58
    Issue number8
    Publication statusPublished - 1993

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    Azides
    Iodides
    Ketones
    Amides
    NAD
    Conformations
    Esters
    Ions
    Derivatives
    Temperature
    triphenylphosphine

    ASJC Scopus subject areas

    • Organic Chemistry

    Cite this

    Syntheses and properties of 5-substituted [n](2,4)pyridinophanes, model compounds of NAD(P). / Oikawa, Tadayoshi; Kanomata, Nobuhiro; Tada, Masaru.

    In: Journal of Organic Chemistry, Vol. 58, No. 8, 1993, p. 2046-2051.

    Research output: Contribution to journalArticle

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    abstract = "[n](2,4)Pyridinophane derivatives 5-8 having an ester or an amide group at the 5-position were synthesized by aza-Wittig reactions between β-substituted vinyliminophosphoranes and cyclic α,β-unsaturated ketones. [β-(Methoxycarbonyl)vinyl]- (1), [β-(N,N-tetramethylenecarbamoyl)vinyl]-(2), [β-(N-benzylcarbamoyl)vinyl]- (3), and (β-carbamoylvinyl)iminophosphorane (4) were synthesized from the corresponding vinyl azides and triphenylphosphine. The heptamethylene chains of 5-(methoxycarbonyl)[7](2,4)pyridinophane (5), 5-(N,N-tetramethylenecarbamoyl)[7](2,4)pyridinophane (6), and 5-(N-benzylcarbamoyl)[7](2,4)pyridinophane (7) flipped with ΔG‡ = 11.2 (Tc = 10.3°C), 10.8 (Tc = 0.2°C), and 10.5 kcal/mol (Tc = -5.2°C), respectively. At lower temperatures, the three conformations of the heptamethylene bridge were frozen. Methylpyridinium iodides 10 (n = 7, 6, and 5) derived from 6 were reduced more easily [E1/2* (half height potential) = -1.65 V (n = 7); -1.63 V (n = 6); -1.29 V va Ag/AgCl (n = 5)] than the reference compound, 2,4-diethyl-5-(N,N-tetramethylenecarbamoyl)pyridinium ion (11) [E1/2* = -1.82 V vs Ag/AgCl]. The reduced species dimerized quickly.",
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    N2 - [n](2,4)Pyridinophane derivatives 5-8 having an ester or an amide group at the 5-position were synthesized by aza-Wittig reactions between β-substituted vinyliminophosphoranes and cyclic α,β-unsaturated ketones. [β-(Methoxycarbonyl)vinyl]- (1), [β-(N,N-tetramethylenecarbamoyl)vinyl]-(2), [β-(N-benzylcarbamoyl)vinyl]- (3), and (β-carbamoylvinyl)iminophosphorane (4) were synthesized from the corresponding vinyl azides and triphenylphosphine. The heptamethylene chains of 5-(methoxycarbonyl)[7](2,4)pyridinophane (5), 5-(N,N-tetramethylenecarbamoyl)[7](2,4)pyridinophane (6), and 5-(N-benzylcarbamoyl)[7](2,4)pyridinophane (7) flipped with ΔG‡ = 11.2 (Tc = 10.3°C), 10.8 (Tc = 0.2°C), and 10.5 kcal/mol (Tc = -5.2°C), respectively. At lower temperatures, the three conformations of the heptamethylene bridge were frozen. Methylpyridinium iodides 10 (n = 7, 6, and 5) derived from 6 were reduced more easily [E1/2* (half height potential) = -1.65 V (n = 7); -1.63 V (n = 6); -1.29 V va Ag/AgCl (n = 5)] than the reference compound, 2,4-diethyl-5-(N,N-tetramethylenecarbamoyl)pyridinium ion (11) [E1/2* = -1.82 V vs Ag/AgCl]. The reduced species dimerized quickly.

    AB - [n](2,4)Pyridinophane derivatives 5-8 having an ester or an amide group at the 5-position were synthesized by aza-Wittig reactions between β-substituted vinyliminophosphoranes and cyclic α,β-unsaturated ketones. [β-(Methoxycarbonyl)vinyl]- (1), [β-(N,N-tetramethylenecarbamoyl)vinyl]-(2), [β-(N-benzylcarbamoyl)vinyl]- (3), and (β-carbamoylvinyl)iminophosphorane (4) were synthesized from the corresponding vinyl azides and triphenylphosphine. The heptamethylene chains of 5-(methoxycarbonyl)[7](2,4)pyridinophane (5), 5-(N,N-tetramethylenecarbamoyl)[7](2,4)pyridinophane (6), and 5-(N-benzylcarbamoyl)[7](2,4)pyridinophane (7) flipped with ΔG‡ = 11.2 (Tc = 10.3°C), 10.8 (Tc = 0.2°C), and 10.5 kcal/mol (Tc = -5.2°C), respectively. At lower temperatures, the three conformations of the heptamethylene bridge were frozen. Methylpyridinium iodides 10 (n = 7, 6, and 5) derived from 6 were reduced more easily [E1/2* (half height potential) = -1.65 V (n = 7); -1.63 V (n = 6); -1.29 V va Ag/AgCl (n = 5)] than the reference compound, 2,4-diethyl-5-(N,N-tetramethylenecarbamoyl)pyridinium ion (11) [E1/2* = -1.82 V vs Ag/AgCl]. The reduced species dimerized quickly.

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