RESUMO
(4E,8E,10E)-9-Methyl-4,8,10-sphingatrienine, a core component of marine sphingolipids, was synthesised for the first time using a copper(I)-mediated 1,2-metallate rearrangement of a lithiated glycal as a key step. It was converted to phalluside-1, a cerebroside isolated from the ascidian Phallusia fumigate. By an analogous route, (4E,8E)-9-methyl-4,8-sphingadiene was synthesised and converted to Sch II, a cerebroside that induces fruiting body formation in the basidiomycete Schizophyllum commune.
Assuntos
Cerebrosídeos/síntese química , Schizophyllum/química , Urocordados/química , Animais , Cerebrosídeos/química , Estrutura MolecularRESUMO
Caught in the middle: The ionomycin calcium complex (see structure; O red, Ca green) was the target of an approach featuring the efficient asymmetric synthesis of an allene by a copper(I)-mediated anti-selective S(N)2' reaction, a highly stereoselective gold(III)-catalyzed cycloisomerization of an alpha-hydroxyallene, and a Rh-catalyzed rearrangement of an alpha-diazo-beta-hydroxyketone.
Assuntos
Cálcio/química , Ionomicina/química , Antibacterianos/química , Catálise , Ciclização , Ouro/química , EstereoisomerismoRESUMO
Key steps in the synthesis of the C1-C16 polyketide fragment of ionomycin were the nucleophilic addition of an organocuprate to a neutral (eta3-allyl)iron complex and the construction of a beta-diketone moiety by the Rh-catalysed rearrangement of an alpha-diazo-beta-hydroxyketone.
Assuntos
Compostos Alílicos , Ionomicina/química , Ionomicina/síntese química , Ferro , Indicadores e Reagentes , Espectroscopia de Ressonância Magnética , Modelos Moleculares , Conformação Molecular , EstereoisomerismoRESUMO
An asymmetric synthesis of the tubulin polymerisation inhibitor (S)-(-)-N-acetylcolchinol is reported based on an intramolecular biaryl oxidative coupling of a 1,3-diarylpropyl acetamide intermediate using phenyliodonium bis(trifluoroacetate) as the final step. Three syntheses of the penultimate 1,3-diarylpropyl acetamide intermediate (S)-(-)-N-[1-[3-(tert-butyldimethylsilyloxy)phenyl)]-3-(3,4,5-trimethoxyphenyl)propyl] acetamide are described which differ in the means by which the stereogenic centre was introduced.
Assuntos
Colchicina/análogos & derivados , Acetamidas/química , Colchicina/síntese química , Colchicina/química , Cristalografia por Raios X , Estrutura Molecular , Oniocompostos/química , Oxirredução , Estereoisomerismo , Moduladores de Tubulina/síntese química , Moduladores de Tubulina/químicaRESUMO
Two adjacent stereogenic centres and a pendant alkene were constructed via nucleophilic addition of a 1,3-dioxan-4-ylcopper(I) reagent to a cationic eta3-allylmolybdenum complex as part of a synthesis of (2E,5S,6R,7E)-6-methyl-8-phenylocta-2,7-dienoic acid, a key component of the Cryptophycins. Oxidative addition of Mo(CO)(4)(THF)(2) to allyl benzoates provides an efficient synthesis of eta3-allylmolybdenum(dicarbonyl) complexes.
Assuntos
Cobre/química , Dioxanos/química , Molibdênio/química , Compostos Organometálicos/química , Peptídeos Cíclicos/química , Compostos Alílicos/química , Antineoplásicos/química , Cátions/química , Depsipeptídeos , Ésteres/síntese química , Ésteres/química , Estrutura Molecular , Oxirredução , EstereoisomerismoRESUMO
An enantiospecific synthesis of the phospholipase A(2) inhibitor (+)-(4R)-manoalide is reported in which all 25 carbons of the sesterterpenoid skeleton are constructed from 3-furaldehyde, trimethylalane, oxirane, CO, beta-ionone, and propargyl bromide. The overall yield for the longest linear sequence (12 steps) is 12%. Key steps include (a) a zirconium-catalyzed carboalumination reaction to construct the C10-C11 trisubstituted alkene, (b) a Cu(I)-mediated 1,2-metalate rearrangement to construct the C6-C7 trisubstituted alkene, (c) a Sharpless kinetic resolution to secure the (4R)-stereochemistry, (d) generation of a 5-stannyl-2,3-dihydrofuran by Mo-catalyzed cycloisomerization of a homopropargylic alcohol, and (e) construction of the hydroxyfuranone ring by photooxidation of a silylfuran.
Assuntos
Alcenos/síntese química , Cobre/química , Terpenos/síntese química , Alcenos/análise , Animais , Catálise , Ciclização , Cinética , Espectroscopia de Ressonância Magnética , Estrutura Molecular , Oxirredução , Poríferos/química , Estereoisomerismo , Terpenos/análise , Zircônio/químicaRESUMO
A 1,2-metallate rearrangment of a higher order cuprate derived from an alpha-lithiated xylal derivative and tridecyllithium is the key step in a synthesis of D-erythro-sphingosine and ceramide. A convenient method for preparing alpha-lithiated glycals from alpha-phenylsulfinyl glycals is also described.
Assuntos
Ceramidas/síntese química , Esfingosina/síntese química , Cobre/química , Xilose/químicaRESUMO
The cyclic pentapeptide c(RGDfK), a selective ligand for the alpha(v)beta3 integrin, was synthesised on solid phase. All synthetic operations including the cyclisation step and the appendage of the Bolton-Hunter reagent was conducted on-resin.