Rearrangements during the acylation of vicinal dianions

Smith, J. G.; Simpson, George Eric

doi:10.1016/s0040-4039(01)97159-x

Cited by 6 publications

(1 citation statement)

References 5 publications

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“…We were unable to react enolizable aliphatic nitriles such as acetonitrile with nitrosamine anions. In contrast, aromatic nitriles afford the u-triazoles ( 6 7 ) and (68) in the yields shown, provided that the metalated nitrosamine is employed n = 1, 2,3 (69) (70) in a twofold excess. A 1 : 1 reaction furnishes only 35-55 of these heterocycles.…”

Section: O-triazoles By Reaction With Nitriles[71* "9 891mentioning

confidence: 96%

Umpolung of Amine Reactivity. Nucleophilic α‐(Secondary Amino)‐alkylation via Metalated Nitrosamines

Seebàch¹,

Enders²

1975

Angew. Chem. Int. Ed. Engl.

206

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There are basically two kinds of hetero atoms in organic molecules: one kind confers electrophilic character upon the carbon atom to which it is bound, and the other kind turns it into a nucleophilic site. The development of methods permitting transitions between the two resulting categories of reagents has become an important task of modern organic synthesis. The scope of such umpolung of the reactivity of functional groups is discussed for the case of amines as an example. A method of preparing masked u-secondary amino carbanions consists in nitrosation of the secondary amine, followed by metalation of the resulting nitrosamine CL to the nitrogen, reaction with electrophiles, and subsequent denitrosation. Many examples are given for each of these steps which illustrate the wide scope of the overall synthetic operation (electrophilic substitution at the a-C atom of the secondary amine). Preliminary applications and a method for avoiding the handling of nitrosamines are presented, and the report concludes with a brief account of the significance of nitrosamines in the study of carcinogenesis and mutagenesis. Table 2. Examples for umpolung of carbonyl compounds and amines. Newly formed bonds are shown in bold print. Attack Reagent Equivalent Product type Ref.

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Section: O-triazoles By Reaction With Nitriles[71* "9 891mentioning

confidence: 96%

Umpolung of Amine Reactivity. Nucleophilic α‐(Secondary Amino)‐alkylation via Metalated Nitrosamines

Seebàch¹,

Enders²

1975

Angew. Chem. Int. Ed. Engl.

206

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ChemInform Abstract: UMLAGERUNGEN BEI DER ACYLIERUNG VON VICINALEN DIANIONEN

Smith¹,

Simpson²

1971

Chemischer Informationsdienst. Organische Chemie

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The reductive metalation of 9‐phenylacridine

Smith

Fogg

1985

Journal of Heterocyclic Chem

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The reductive metalation of 9‐phenylacridine by sodium to a dianion is described and the reactions of the dianion with electrophiles investigated. Reactions of the dianion with methanol, dimethyl sulfate, X(CH2)nX (n = 2,3,4, X = Cl, Br), and methyl chloroformate were studied. Reactions occurred exclusively at the 9 and 10 positions forming 9,10‐dihydro‐9‐phenylacridine derivatives. Of particular interest was the fact that the dianion was dialkylated with 1,2‐dichloroethane but monoalkylated at the 9‐position with 1,3‐dichloropropane and 1,4‐dichlorobutane. These results are compared to those obtained with dianions derived from other heterocyclic systems and analyzed using Baldwin's Rules for Ring Closure.

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Rearrangements during the acylation of vicinal dianions

Cited by 6 publications

References 5 publications

Umpolung of Amine Reactivity. Nucleophilic α‐(Secondary Amino)‐alkylation via Metalated Nitrosamines

Umpolung of Amine Reactivity. Nucleophilic α‐(Secondary Amino)‐alkylation via Metalated Nitrosamines

ChemInform Abstract: UMLAGERUNGEN BEI DER ACYLIERUNG VON VICINALEN DIANIONEN

The reductive metalation of 9‐phenylacridine

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