A synthetic method for direct conversion of ketones into cyanides. Introduction of a one carbon unit.

Oldenziel, O. H.; Leusen, A. M. Van

doi:10.1016/s0040-4039(01)95942-8

Cited by 54 publications

(9 citation statements)

References 13 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…There are various methodologies in the literature for the homologation of a ketone to a secondary carboxylic acid in two or three steps. Representative methodologies have involved intermediates such as enol ethers, epoxides, cyanohydrins, α,β-unsaturated sulfones, ketene thioacetals, glycidic esters, nitriles, and α-acetoxyacrylonitriles to add the one-carbon unit. These existing methodologies have been limited by their high cost or low efficiency and throughput for a scalable process.…”

mentioning

confidence: 99%

Rearrangement of Epoxynitriles: A Convenient Homologation of Acyclic and Cyclic Ketones to Carboxylic Acids

Badham

Mendelson

et al. 2002

J. Org. Chem.

View full text Add to dashboard Cite

A convenient two-step homologation of both aliphatic and aromatic ketones to the corresponding carboxylic acid has been developed. First ketones were converted to epoxynitriles with the Darzens reaction. Second, a Lewis acid mediated rearrangement of these epoxynitriles with lithium bromide was achieved to give homologated secondary alkanoic acids (as well as aryl-alkanoic) in good yields. The mechanism and the scope of the rearrangement reaction were investigated. This strategy constitutes a two-step homologation of ketones to secondary carboxylic acids.

show abstract

mentioning

confidence: 99%

Rearrangement of Epoxynitriles: A Convenient Homologation of Acyclic and Cyclic Ketones to Carboxylic Acids

Badham

Mendelson

et al. 2002

J. Org. Chem.

View full text Add to dashboard Cite

show abstract

“…(2) In addition to 2a, ethyl formate (11) has been detected qualitatively (RO" = EtO-), which accounts for the fate of the isocyano carbon of 1. (3) The reaction can be interrupted at the stage of 7 as well as 8 to give 13 or 14. (4) Under the conditions of reaction 1 both 13 and 14 can be converted to 2, and further also 13 to 14 (R1 -R2 = pentamethylene).…”

mentioning

confidence: 99%

Chemistry of sulfonylmethyl isocyanides. 13. A general one-step synthesis of nitriles from ketones using tosylmethyl isocyanide. Introduction of a one-carbon unit

Oldenziel¹,

Vanleusen²,

Leusen³

1977

J. Org. Chem.

207

129

View full text Add to dashboard Cite

Ketones are converted efficiently, in one step, to nitriles (R2CO -R2CHC=N) at temperatures between 0 and 45 O C by the use of TosMIC (tosylmethyl isocyanide) and base. This conversion is effectively a reductive cyanation, unlike the classical cyanohydrin reaction. The reaction is shown to be generally applicable.Tosylmethyl isocyanide (TosMIC, 1) is a synthon with diverse and steadily expanding applications. Thus far emphasis in the chemistry of TosMIC has centered mainly on heterocyclic synthesis. The preceding paper in this series deals with the synthesis of imidazoles from TosMIC and aldimines,2a and summarizes other azole (and azoline) syntheses.2 The present paper will show, however, that the application of TosMIC by no means is restricted to the domain of heterocyclic synthesis only.We here wish to concentrate on the use of TosMIC in an efficient, direct conversion of ketones to nitriles3 2

show abstract

“…There are various methodologies in the literature for the homologation of a ketone to a secondary carboxylic acid in two or three steps. Representative methodologies have involved intermediates such as enol ethers, epoxides, cyanohydrins, α,β-unsaturated sulfones, glycidic esters, and nitriles, to add the one-carbon unit. However, most transformations are not amenable to scale-up.…”

Section: Resultsmentioning

confidence: 99%

A Practical Synthesis of the PDE4 Inhibitor, SB-207499, from a Cyclohexanone Precursor

Badham

Chen

Cummings

et al. 2002

Org. Process Res. Dev.

View full text Add to dashboard Cite

show abstract

A synthetic method for direct conversion of ketones into cyanides. Introduction of a one carbon unit.

Cited by 54 publications

References 13 publications

Rearrangement of Epoxynitriles: A Convenient Homologation of Acyclic and Cyclic Ketones to Carboxylic Acids

Rearrangement of Epoxynitriles: A Convenient Homologation of Acyclic and Cyclic Ketones to Carboxylic Acids

Chemistry of sulfonylmethyl isocyanides. 13. A general one-step synthesis of nitriles from ketones using tosylmethyl isocyanide. Introduction of a one-carbon unit

A Practical Synthesis of the PDE4 Inhibitor, SB-207499, from a Cyclohexanone Precursor

Contact Info

Product

Resources

About