The Synthesis of Thiol Esters with Dicyclohexylcarbodiimide

Grunwell, John R.; Foerst, Denis L.

doi:10.1080/00397917608065595

Cited by 38 publications

(3 citation statements)

References 3 publications

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“…0.1 0% (v/v) TFA to methanol, followed by chromatography on a S Iu Supelco Cl8 column and the same gradient, yielding [3H]DACA that was greater than 90 % pure (specific radioactivity -0.1 Ci/mmol). An Synthesis of 4-trans-(NN-dimethylamino)cinnamoyl derivatives 4-trans-(NN-Dimethylamino)cinnamoyl-N-acetylcysteine was prepared by the method of Grunwell & Foerst (1976); unlabelled DACI was prepared by the method of Breaux & Bender (1976;m.p. 163-167°C); 4-trans-(NN-dimethylamino)cinnamoyl ethyl ester was prepared as described by Pfeiffer & Haefelin (1922; m.p.…”

Section: Purification Of I'hidacamentioning

confidence: 99%

Aldehyde dehydrogenase. Covalent intermediate in aldehyde dehydrogenation and ester hydrolysis

Blatter

Abriola

Pietruszko

1992

Biochemical Journal

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4-trans-(NN-Dimethylamino)cinnamaldehyde (an aldehyde, DACA) and 4-trans-(NN-dimethylamino)cinnamoylimidazole (an amide, DACI) have been shown to be substrates for human aldehyde dehydrogenase (EC 1.2.1.3) which form chromophoric covalent intermediates. The spectra of covalent intermediates from both the cytoplasmic (E1) and mitochondrial (E2) isoenzymes derived from DACA and DACI were compared. The spectra were similar when either substrate was used, and also when the two isoenzymes were compared, and resembled that obtained for 4-trnas-(NN-dimethylamino)cinnamoyl-N-acetylcysteine, but differed from the spectrum of 4-trans-(NN-dimethylamino)cinnamoyl ethyl ester. After extensive digestion of the covalent intermediates from both 3H-labelled DACA and DACI with Pronase and purification, the labelled amino acid was identified as cysteine. Covalent intermediates from both DACA and DACI were also digested with trypsin, and labelled peptides were purified by ion-exchange and reverse-phase chromatography. Amino acid sequence analysis showed that the peptide comprising residues 273-307 was labelled by both DACA and DACI. The radioactive label at cysteine residues 301-303 of the primary structure could be unequivocally identified by employing the DACA derivative. Assignment of label to cysteine-302 was achieved by employing iodoacetamide-labelled E1 isoenzyme (iodoacetamide specifically labels cysteine-302), in which case there was no formation of the covalent intermediate from either DACA or DACI. In addition, cysteine-302 is the only cysteine residue conserved in all aldehyde dehydrogenases sequenced. Thus cysteine-302 is the amino acid residue that forms a covalent intermediate with both aldehyde and ester substrates.

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Section: Purification Of I'hidacamentioning

confidence: 99%

Aldehyde dehydrogenase. Covalent intermediate in aldehyde dehydrogenation and ester hydrolysis

Blatter

Abriola

Pietruszko

1992

Biochemical Journal

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“…Subsequently, an alternative and more efficient route to 48 was devised, in which the mesylate 46 was treated with potassium thioacetate and the resultant thioester was converted to thiol 49 with sodium methoxide in methanol. Coupling of 49 with (2 R ,3 S )- 8 in the presence of DCC and DMAP afforded 48 in an overall 73% yield from 46 . The final cyclization of 48 to curacin A ( 1 ) was effected by cleavage of the Boc group with trifluoroacetic acid to furnish the corresponding ammonium trifluoroacetate salt, which was subjected to refluxing benzene without isolation.…”

Section: Synthesis Of Curacin Amentioning

confidence: 99%

Absolute Configuration and Total Synthesis of (+)-Curacin A, an Antiproliferative Agent from the Cyanobacterium Lyngbya majuscula

1997

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The absolute configuration of curacin A was determined as (2R,13R,19R,21S)-1 by comparison of degradation products 2 and 3 with the same materials prepared by asymmetric synthesis. The total synthesis of 1 was completed from (1R,2S)-2-methylcyclopropanecarboxylic acid (8) and the amino alcohol derivative 46. The latter was prepared from 4-pentynal (14) and the Garner aldehyde (43). Asymmetric allylation of 14 followed by methylation of the derived alcohol 16 gave 17, which was subjected to zirconation−iodination to yield 18. The latter was coupled to the vinyl boronate 21, prepared from 4-pentynyl acetate (20), in the presence of Pd(0), and the resultant trienol 22 was converted to phosphonium iodide 24. Wittig reaction of the ylide from 24 with 43 afforded tetraene 44 which produced 45 upon methanolysis. The mesylate 46 was advanced to thioester 48 either by direct coupling with potassium thiolate 47 obtained from (−)-8 or indirectly via 49. The amino thioester liberated from 48 underwent thermal cyclization to give (+)-curacin A.

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“…5 The most traditional methods for the preparation of thiolesters involve either the coupling of a thiol with a carboxylic acid or an alcohol with a thiolcarboxylic acid. However, it has been found that the former strategy needs long reaction times 6 and the latter needs the participation of dehydrating agents such as DCC, 7 due to the small equilibrium constants. The reaction of alkyl halides with zinc thiolacetate has also been reported as an alternative approach.…”

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confidence: 99%

A facile and practical method for the preparation of thioacetates from alkyl halides and sodium thioacetate catalysed by PEG400

Cao

Chen

et al. 2004

Journal of Chemical Research

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The Synthesis of Thiol Esters with Dicyclohexylcarbodiimide

Cited by 38 publications

References 3 publications

Aldehyde dehydrogenase. Covalent intermediate in aldehyde dehydrogenation and ester hydrolysis

Aldehyde dehydrogenase. Covalent intermediate in aldehyde dehydrogenation and ester hydrolysis

Absolute Configuration and Total Synthesis of (+)-Curacin A, an Antiproliferative Agent from the Cyanobacterium Lyngbya majuscula

A facile and practical method for the preparation of thioacetates from alkyl halides and sodium thioacetate catalysed by PEG400

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