1,3-Anionische Cycloaddition von 2-Azaallyllithiumverbindungen an Nitrile

Kauffmann, Thomas; Busch, Alfred; Habersaat, Kai; Köppelmann, Edgar

doi:10.1002/ange.19730851307

Cited by 15 publications

(6 citation statements)

References 5 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The i.r. spectra of these compounds show strong absorptions Ph Ar Ph ( 1 ) ( 2 ) .Ph A r ' Ar ' CO, (4 1 ca. 1730 cm-' which are consistent with the presence of enol ester groups.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Aroylation of carbanions derived from N-(diphenylmethyl)arylmethanimines. A synthesis of 4-aroyloxy-2-azabuta-1,3-dienes

Armesto¹,

Ortiz²,

Perez‐Ossorio³

1986

J. Chem. Soc., Perkin Trans. 1

View full text Add to dashboard Cite

The acylation of carbanions derived from N-(diphenylmethyl)arylmethanimines using aroyl chlorides, allows the preparation of a new type of substituted 2-azabuta-l,3-dienes in which the imino group is conjugated with an enol ester. The reaction is quite general and facilitates the preparation of a wide range of 2-azadienes with electron-donating and electron-withdrawing groups on the phenyl rings. The site selectivity for the attack of the electrophile on the aza-ally1 anion can be controlled by the substituents on the carbanion and on the hardness of the electrophile.

show abstract

“…The i.r. spectra of these compounds show strong absorptions Ph Ar Ph ( 1 ) ( 2 ) .Ph A r ' Ar ' CO, (4 1 ca. 1730 cm-' which are consistent with the presence of enol ester groups.…”

Section: Resultsmentioning

confidence: 99%

“…We wish to report the generation of carbanions (1) derived from N-(diphenylmethy1)arylmethanimines (2) and their trapping using p-substituted benzoyl chlorides (3). The influence of electronic and steric factors in the carbanion on the site selectivity of the reaction and the influence of the hardness of the electrophile have been studied.…”

mentioning

confidence: 99%

Aroylation of carbanions derived from N-(diphenylmethyl)arylmethanimines. A synthesis of 4-aroyloxy-2-azabuta-1,3-dienes

Armesto¹,

Ortiz²,

Perez‐Ossorio³

1986

J. Chem. Soc., Perkin Trans. 1

View full text Add to dashboard Cite

show abstract

“…See Experimental Section for reaction conditions. 6 Unknown product. c Although quenching conditions in this experiment were identical with the preceding one, the reaction was performed on a preparative scale and at -20°rather than 25°.…”

Section: Resultsmentioning

confidence: 99%

“…A-Lithioc«-2,3-diphenylaziridine opened in conrotatory fashion to cú,?ronj-l,3-diphenyl-2-azaallyllithium, and was trapped in situ as a cycloadduct with zmny-stilbene. 6 Along with the major product shown in eq 3, a minor…”

mentioning

confidence: 97%

Ring openings of dilithium derivatives of 2,3-diphenylcyclopropane-1-carboxylic acids

Ford

Newcomb

1973

J. Am. Chem. Soc.

View full text Add to dashboard Cite

2,3-Diphenylcyclopropane-l-carboxylic acids undergo ring opening when treated with lithium diisopropylamide (LDIA) in tetrahydrofuran. From c/j,tra«i-2,3-diphenylcyclopropane-l-carboxylic acid (la) LDIA treatment, hydrolysis, and diazomethane esterification produce methyl cis-and nww-a-benzylcinnamates (6b and 4b). From /m/«,i/'u/K-2,3-diphenylcyclopropane-l-carboxylic acid (2a) the same procedure gives methyl (£)-and (Z)-3,4-diphenyl-3-butenoates (7b and 8b). Similar treatment of 2,3:4,5-dibenzo-2,4-norcaradiene-a«n'-7-carboxylic acid (3a) produces methyl 9-phenanthrylacetate (lib) and methyl 3,4:5,6-dibenzocyclohepta-l,3,5-triene-l-carboxylate (12b). Structures of all of the ring-opened products have been verified by their spectral properties and independent syntheses. All of them can be explained by electrocyclic conversions of cyclopropyl anions to allyl anions. Conversion of 3a to 12b can proceed only by a disrotatory path, while the other ring openings should be conrotatory according to theory. Preliminary kinetic experiments suggest that the rate-limiting step for ring opening of la is loss of the second proton from the lithium carboxylate, while the rate-limiting steps for ring openings of 2a and 3a may be the ring opening itself. The relative rates of conversion of the cyclopropanecarboxylic acids to ring-opened materials are la » 2a » 3a. In contrast to the slow deprotonation of la, 2a, and 3a, methyl c/s',//-tim-2,3-diphenylcyclopropane-l-carboxylate (lb) forms an enolate with LDIA in THF readily at -78°. The lithium enolate of lb appears to undergo ring opening at -39°. The name dilithium "carboxylate enolate" is proposed for ciilithio derivatives of aliphatic carboxylic acids which are formed by loss of protons from oxygen and a carbon.

show abstract

“…The Schiff base 1 is known to be useful synthon in organic synthesis under both anhydrous [3][4][5][6] and aqueous [7][8][9] conditions. An optimisation study of the reaction of 1 with methyl cinnamate (2a) revealed that better yields and stereoselectivity for the adduct 3a was obtained when the reaction was performed at room temperature for one hour using acetonitrile as a solvent, with 50% NaOH and TEBA (67% yield of 3a).…”

mentioning

confidence: 99%

A Convenient Synthesis of Threo-4-Amino-3, 4-Diphenylbutanoic Acid and Its Derivatives¹

Dryanska

Pashkuleva

Angelov

2003

Journal of Chemical Research

View full text Add to dashboard Cite

show abstract

1,3-Anionische Cycloaddition von 2-Azaallyllithiumverbindungen an Nitrile

Cited by 15 publications

References 5 publications

Aroylation of carbanions derived from N-(diphenylmethyl)arylmethanimines. A synthesis of 4-aroyloxy-2-azabuta-1,3-dienes

Aroylation of carbanions derived from N-(diphenylmethyl)arylmethanimines. A synthesis of 4-aroyloxy-2-azabuta-1,3-dienes

Ring openings of dilithium derivatives of 2,3-diphenylcyclopropane-1-carboxylic acids

A Convenient Synthesis of Threo-4-Amino-3, 4-Diphenylbutanoic Acid and Its Derivatives¹

Contact Info

Product

Resources

About

1,3-Anionische Cycloaddition von 2-Azaallyllithiumverbindungen an Nitrile

Cited by 15 publications

References 5 publications

Aroylation of carbanions derived from N-(diphenylmethyl)arylmethanimines. A synthesis of 4-aroyloxy-2-azabuta-1,3-dienes

Aroylation of carbanions derived from N-(diphenylmethyl)arylmethanimines. A synthesis of 4-aroyloxy-2-azabuta-1,3-dienes

Ring openings of dilithium derivatives of 2,3-diphenylcyclopropane-1-carboxylic acids

A Convenient Synthesis of Threo-4-Amino-3, 4-Diphenylbutanoic Acid and Its Derivatives1

Contact Info

Product

Resources

About

A Convenient Synthesis of Threo-4-Amino-3, 4-Diphenylbutanoic Acid and Its Derivatives¹