Horner-Wadsworth-Emmons olefination of nonstabilized phosphonates. A new synthetic approach to β,γ-unsaturated amides

Janecki, Tomasz; Bodalski, R.; Micha,; Wieczorek, kl; Bujacz, G.

doi:10.1016/0040-4020(94)01046-3

Cited by 18 publications

(6 citation statements)

References 13 publications

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“…The E stereochemistry in the CC bond was assigned on the basis of the value of 1 H NMR coupling constant between the olefinic protons of compounds 3 in the case of compounds 3a − p , and by comparison of the NMR spectra for compounds 3a , , 3d , 3e , 3i ,16b 3j , 3 l , ,16a and 3n 16a with those described in the literature for the same unsaturated amides. In the case of trisubstituted amides 3q − w , the total stereoselectivity was again observed and ascertained as above.…”

Section: Resultsmentioning

confidence: 99%

Sequential Reactions Promoted by Manganese: Completely Stereoselective Synthesis of (E)-α,β-Unsaturated Amides, Ketones, Aldehydes, and Carboxylic Acids

2007

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A complete E-selective synthesis of alpha,beta-unsaturated amides through a sequential reaction of a range of dichloroamides with a variety of aldehydes promoted by Rieke manganese (Mn*) is reported. A mechanism based on a sequential aldol-type reaction and a completely stereoselective beta-elimination is proposed to explain these results. The unsaturated amides obtained are readily and efficiently transformed into alpha,beta-unsaturated ketones, aldehydes, or carboxylic acids without loss of the diastereoisomeric purity of the C-C double bond.

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Section: Resultsmentioning

confidence: 99%

Sequential Reactions Promoted by Manganese: Completely Stereoselective Synthesis of (E)-α,β-Unsaturated Amides, Ketones, Aldehydes, and Carboxylic Acids

2007

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“…IR spectra: Perkin-Elmer 881 instrument, in cm -1 . NMR spectra: JEOL Lambda-270-MHz instrument: 1 H at 270 MHz, 13 C at 67.5 MHz, δ in ppm, and J in Hz, with TMS as an internal standard. EIMS: V.G.-Autospec instrument equipped with a Fisons autosampler; EI at 70 eV; m/z (rel %).…”

Section: Methodsmentioning

confidence: 99%

“…Having discovered that 4-(4‘-chlorophenyl)-2-butenoic acid ( 10 ) could not readily be isolated, owing to its preference to isomerize to 9 , an alternative strategy to the routine acylation approach was required for the preparation of 5e (Scheme ). The protocol selected involved the formation of the α,β-unsaturated amide via a Horner−Wadsworth−Emmons-type reaction . Acylation of 7b using diethoxyphosphorylacetyl chloride , afforded 11 .…”

Section: Chemistrymentioning

confidence: 99%

“…The protocol selected involved the formation of the R,βunsaturated amide via a Horner-Wadsworth-Emmons-type reaction. 13 Acylation of 7b using diethoxyphosphorylacetyl chloride 14,15 afforded 11. Treatment of 11 with LDA at low temperature in the presence of 4-chlorophenylacetaldehyde afforded 5e exclusively in the (E)-configuration.…”

Section: Introductionmentioning

confidence: 99%

“…Supporting Information Available: 1 H NMR, 13 C NMR, mass spectra, infrared, melting point, and microanalysis data. This material is available free of charge via the Internet at http:// pubs.acs.org.…”

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confidence: 99%

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Structural Determinants of Opioid Activity in Derivatives of 14-Aminomorphinones: Effects of Changes to the Chain Linking of the C₁₄-Amino Group to the Aryl Ring

et al. 2006

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The 14-aminodihydromorphinone and codeinone series of opioid ligands have produced a number of ligands of substantial interest. In order to investigate the importance of the 14-substituent a series of analogues in which the side chain length is varied and the amide and alkene functions are reduced have been prepared. Binding affinity, particularly at the mu opioid receptor (MOR), was largely determined by the aromatic group of the side chain. In the [ 35 S]GTPγS functional assay, the ligands having a three carbon side chain were more potent antagonists than their longer chain counterparts, whilst shorter, 2 carbon chain analogues were of higher MOR efficacy, an effect that was confirmed in vivo. Wash-resistant binding was observed within this series and appeared to be unrelated to side chain length.

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Synthesis of (E)-α,β-Unsaturated Amides with High Selectivity by Using Samarium Diiodide

2001

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Stereoselective beta-elimination of 2-chloro-3-hydroxyamides 1 is achieved by using samarium diiodide to yield alpha,beta-unsaturated amides 2, in which the C=C bond is di- tri-, or tetrasubstituted. The starting compounds 1 are easily prepared by reaction of the corresponding lithium enolates of alpha-chloroamides with aldehydes or ketones at - 78 degrees C. The influence of the reaction conditions and the structure of the starting compounds on the stereoselectivity of the beta-elimination reaction is also discussed.

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Horner-Wadsworth-Emmons olefination of nonstabilized phosphonates. A new synthetic approach to β,γ-unsaturated amides

Cited by 18 publications

References 13 publications

Sequential Reactions Promoted by Manganese: Completely Stereoselective Synthesis of (E)-α,β-Unsaturated Amides, Ketones, Aldehydes, and Carboxylic Acids

Sequential Reactions Promoted by Manganese: Completely Stereoselective Synthesis of (E)-α,β-Unsaturated Amides, Ketones, Aldehydes, and Carboxylic Acids

Structural Determinants of Opioid Activity in Derivatives of 14-Aminomorphinones: Effects of Changes to the Chain Linking of the C₁₄-Amino Group to the Aryl Ring

Synthesis of (E)-α,β-Unsaturated Amides with High Selectivity by Using Samarium Diiodide

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Horner-Wadsworth-Emmons olefination of nonstabilized phosphonates. A new synthetic approach to β,γ-unsaturated amides

Cited by 18 publications

References 13 publications

Sequential Reactions Promoted by Manganese: Completely Stereoselective Synthesis of (E)-α,β-Unsaturated Amides, Ketones, Aldehydes, and Carboxylic Acids

Sequential Reactions Promoted by Manganese: Completely Stereoselective Synthesis of (E)-α,β-Unsaturated Amides, Ketones, Aldehydes, and Carboxylic Acids

Structural Determinants of Opioid Activity in Derivatives of 14-Aminomorphinones: Effects of Changes to the Chain Linking of the C14-Amino Group to the Aryl Ring

Synthesis of (E)-α,β-Unsaturated Amides with High Selectivity by Using Samarium Diiodide

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Structural Determinants of Opioid Activity in Derivatives of 14-Aminomorphinones: Effects of Changes to the Chain Linking of the C₁₄-Amino Group to the Aryl Ring