RESUMO
Ajoene is a compound found in garlic extracts exhibiting a large range of biological activity. Novel ajoene analogues have been prepared in the search of compounds with superior bioactivity. Modifications include the alteration of the sulfoxide, the central alkene and the terminal allyl groups.
RESUMO
A short total synthesis of ajoene, (E,Z)-4,5,9-trithiadodeca-1,6,11-triene 9-oxide, has been achieved over sixâ steps. In addition, a continuous flow synthesis under mild reaction conditions to (E,Z)-4,5,9-trithiadodeca-1,7,11-triene is described starting from simple and easily accessible starting materials. Over four steps including propargylation, radical addition of thioacetate, deprotection, and disulfide formation/ allylation, the target product can be obtained at a rate of 0.26â g h-1 in an overall yield of 12 %.
RESUMO
We describe a short total synthesis of ajoene, a major biologically active constituent of garlic. The instability of allicin as the only other known alternative starting material has led to the development of a reliable procedure for the synthesis of ajoene from simple building blocks that is also suitable for upscale operations.
Assuntos
Dissulfetos/química , Dissulfetos/síntese química , Dissulfetos/farmacologia , Alho/química , Alho/metabolismo , Pseudomonas aeruginosa/efeitos dos fármacos , Pseudomonas aeruginosa/fisiologia , Percepção de Quorum/efeitos dos fármacos , Selênio/química , Ácidos Sulfínicos/química , SulfóxidosRESUMO
A series of ab initio calculations are presented on the alkyne-bridged dicobalt hexacarbonyl cluster Co2 micro-C2H2 (CO)6, indicating that this compound has substantial multireference character, which we interpret as evidence of singlet diradical behavior. As a result, standard theoretical methods such as restricted Hartree-Fock (RHF) or Kohn-Sham (RKS) density functional theory cannot properly describe this compound. We have therefore used complete active space (CAS) methods to explore the bonding in and spectroscopic properties of Co2 micro-C2H2 (CO)6. CAS methods identify significant population of a Co-Co antibonding orbital, along with Co-pi* back-bonding, and a relatively large singlet-triplet energy splitting. Analysis of the electron density and related quantities, such as energy densities and atomic overlaps, indicates a small but significant amount of covalent bonding between cobalt centers.
RESUMO
Density functional calculations are used to explore the formation of iminium ions from secondary amines and acrolein and the subsequent reactivity of the resulting iminium ions. After establishing a feasible profile for this reaction in simulated experimental conditions, we focus on the effect of variation in amine structure on calculated barriers. This analysis shows that incorporation of a heteroatom (N or O) in the alpha-position to the reactive amine results in significantly reduced energy barriers, as does an electron-withdrawing group (carbonyl or thiocarbonyl) in the beta-position. Electron density analysis is used to monitor reactions at a detailed level, and to identify important intermolecular interactions at both minima and transition states. Barriers to reaction are linked to calculated proton affinities of secondary amines, suggesting that the relative ease of protonation-deprotonation of the amine is a key property of effective catalysts. Moreover, barriers for subsequent Diels-Alder reaction of iminium ions with cyclopentadiene are lower than for their formation, suggesting that formation may be the rate determining step in the catalytic cycle.