Cyanocarbon Chemistry. XVIII.<sup>1</sup> Tricyanovinylation of Hydrazones and Other Nucleophilic Substances

Roland, J. R.; McKusick, B. C.

doi:10.1021/ja01468a025

Cited by 28 publications

(13 citation statements)

References 3 publications

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“…A third stable product was 1-azulyltricyanoethylene (6, 8.8%), which has been shown to be formed from the reaction of azulene with TCNE13 or chlorotricyanoethylene. 14 The isolation of 6 and the fact that a number of unstable products were observed in other chromatographic fractions is consistent with TCNE being formed from a reaction of TCNEO with azulene wherein the latter is oxidized. An alternative route to 5 would require that the second intermediate (1) leading to 2 exist long enough to react with a second molecule of TCNEO as shown (eq 3).…”

Section: Methodssupporting

confidence: 56%

Reaction of azulene with tetracyanoethylene oxide

Anderson¹,

Kurokawa²

1975

J. Org. Chem.

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Section: Methodssupporting

confidence: 56%

Reaction of azulene with tetracyanoethylene oxide

Anderson¹,

Kurokawa²

1975

J. Org. Chem.

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“…[55] The addition of 96 to acetylenedicarboxylate 99 and to tetracyanoethylene 102 to afford 100 [56] and 101, [57] respectively, have also been documented, but the latter reaction may possibly proceed by an addition-elimination mechanism (Scheme 18). This course is remarkable, because both furan-2-carbaldehyde dimethylhydrazone 96 (X = O) as a good diene exemplified by the synthesis of 103 [58] and the three electrondeficient substrates as dienophiles are well-known partners in the Diels-Alder reaction.…”

Section: Nucleophilic Additions Of Vinylogous Azaenamines To Activatementioning

confidence: 99%

Aldehyde N,N‐Dialkylhydrazones as Neutral Acyl Anion Equivalents: Umpolung of the Imine Reactivity

et al. 2007

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The isoelectronic replacement of the α‐carbon of enamines by nitrogen leads to the corresponding hydrazones, and thus, they can be termed “aza‐enamines”. Hence, aldehyde N,N‐dialkylhydrazones enable analogous electrophilic substitutions at the imine carbon that corresponds to the β‐carbon of enamines. In addition, after hydrolysis of the product hydrazones to the parent ketones or aldehydes, these reactions constitute an umpolung of the classical carbonyl reactivity and overall a nucleophilic acylation or formylation. This review covers the aza‐enamine chemistry from its very beginning in the late 1960s up to this year. In the first part, reactions of aromatic, aliphatic, and heterocyclic aldehyde N,N‐dialkylhydrazones with highly reactive substrates such as the Vilsmeier and Mannich reagents, sulfonyl isocyanates, perfluoroacetic anhydride, and inorganic electrophiles such as halogens and phosphorus tribromide are described. The hydrazones of α,β‐unsaturated aldehydes react as vinylogous aza‐enamines at the terminal carbon providing unsaturated aldehydes. As electron‐rich dienes and dienophiles, they also form Diels–Alder adducts and thus interesting N‐heterocycles. The second part covers carbon–carbon bond formations of the sterically less‐demanding formaldehyde N,N‐dialkylhydrazones with synthetically very useful electrophiles such as various Michael acceptors and carbonyl compounds. Formaldehyde SAMP‐hydrazone and related derivatives generally give excellent asymmetric inductions. Finally, first organocatalytic versions of the aza‐enamine chemistry are presented. In summary, the rich chemistry of aldehyde N,N‐dialkylhydrazones as neutral acyl anion, formyl anion, and cyanide equivalents is demonstrated. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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“…with the elimination of hydrogen cyanide and introduction of a tricyano vinyl group at one of the positions of high electron density (93,114,134). Thus alkylation with TONE of phenanthrene (138), azulene (51), guaizulene (51, 52), and 2,6-dimethylphenol (55,138) are illustrative.…”

Section: XIVmentioning

confidence: 99%

The Chemistry of Tetracyanoethylene

Dhar¹

1967

Chem. Rev.

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Cyanocarbon Chemistry. XVIII.¹ Tricyanovinylation of Hydrazones and Other Nucleophilic Substances

Cited by 28 publications

References 3 publications

Reaction of azulene with tetracyanoethylene oxide

Reaction of azulene with tetracyanoethylene oxide

Aldehyde N,N‐Dialkylhydrazones as Neutral Acyl Anion Equivalents: Umpolung of the Imine Reactivity

The Chemistry of Tetracyanoethylene

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Cyanocarbon Chemistry. XVIII.1 Tricyanovinylation of Hydrazones and Other Nucleophilic Substances

Cited by 28 publications

References 3 publications

Reaction of azulene with tetracyanoethylene oxide

Reaction of azulene with tetracyanoethylene oxide

Aldehyde N,N‐Dialkylhydrazones as Neutral Acyl Anion Equivalents: Umpolung of the Imine Reactivity

The Chemistry of Tetracyanoethylene

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Cyanocarbon Chemistry. XVIII.¹ Tricyanovinylation of Hydrazones and Other Nucleophilic Substances