A novel concept for the direct oxidation of cycloalkanes to the corresponding cyclic ketones in a one‐pot synthesis in water with molecular oxygen as sole oxidizing agent was reported recently. Based on this concept we have developed a new strategy for the double oxidation of n‐heptane to enable a biocatalytic resolution for the direct synthesis of heptanone and (R)‐heptanols in a one‐pot reaction. The bicatalytic cascade employs an NADH driven P450 BM3 monooxygenase variant (WTNADH, 19A12NADH or CM1NADH) and an (S)‐enantioselective alcohol dehydrogenase (RE‐ADH). In the initial step n‐heptane is hydroxylated under consumption of NADH to produce (R/S)‐heptanol. In the second oxidation step the (S)‐heptanol enantiomers are transformed to the corresponding ketones, reducing and thereby regenerating the cofactor. Characterization of initial hydroxylation step revealed high turnover frequencies (TOF) of up to 600 min−1, as well as high coupling efficiencies using NADH as cofactor (up to 44%). In the cascade reaction a nearly 2‐fold improved product formation was achieved, compared to the single hydroxylation reaction. The total product concentration reached 1.1 mM, corresponding to a total turnover number (TTN) of 2500. Implementation of an additional cofactor regeneration system (D ‐glucose/glucose dehydrogenase) enabled a further enhancement in product formation with a total product concentration of 1.8 mM and a TTN of 3500. 相似文献
The PdCl(C3H5)(dppb)/KOAc system was found to be effective for the direct regioselective C‐5 arylation of 3‐acetylpyrroles with ortho‐substituted aryl bromides. This procedure has been found to be tolerant to a variety of functional groups at C‐2 of the aryl bromide such as methyl, formyl, nitrile, nitro, hydroxymethyl, chloro, fluoro or trifluoromethyl. The sequential direct C‐5 arylation followed by C‐2 arylation of such 3‐substituted pyrroles allows the synthesis of 2,5‐diaryl‐3‐acetylpyrroles in high yields. 相似文献
A rhodium(III)‐catalyzed oxidative C H olefination directed by Weinreb amides, a class of well developed versatile building blocks in organic synthesis, has been developed with air as the terminal oxidant. The reactions proceed with excellent reactivity, good functional group tolerance and high yields. 相似文献
An efficient palladium‐catalyzed decarboxylative ortho‐acylation of 2‐aryloxypyridines with α‐oxocarboxylic acids is described. In this new transformation, the aromatic C(sp2) H bond was successfully acylated to give diverse aromatic ketones regioselectively in moderate to good yields. The pyridine group can be removed easily after the acylation to give the corresponding 2‐hydroxy aromatic ketones. 相似文献
Pyrroles, ubiquitous bioactive heterocycles in nature, are readily prepared via a palladium‐catalyzed oxidative annulation of cyclic trans‐enamines to various internal alkynes in the absence of a directing group.
A new rhodium(III)‐catalyzed N‐annulation reaction of benzylamines with internal alkynes has been developed. Observations made during these efforts suggest that the mechanistic pathway followed in this process involves direct participation of benzylamines without their preliminary oxidative dehydrogenation. Moreover, N‐annulation reactions of primary benzylamines result in the formation of mixtures of isoquinolines and 8‐vinylisoquinolines. Finally, secondary and tertiary benzylamines undergo rhodium(III)‐catalyzed N‐annulation reactions to generate the respective isoquinolinium and hydroisoquinolinium salt products.
To establish a system for the efficient one bacterial multi‐enzymatic biosynthesis of both (R)‐ and (S)‐β‐hydroxy nitriles, we co‐expressed alcohol dehydrogenases with opposite stereoselectivities, cofactor regeneration enzymes, and a halohydrin dehalogenase in Escherichia coli. By researching cofactor recycling and various co‐expression strategies and by selecting and engineering the halohydrin dehalogenase, we engineered two E. coli strains, which were subsequently used in a cascade of reactions to produce chiral β‐hydroxy nitriles with high enantiomeric excess directly from prochiral α‐halo ketones. Three valuable pharmaceutical intermediates were prepared by means of this catalytic system, and substrate conversion reached about >99%. More importantly, the system is of low cost because there is no need for expensive cofactors or for expression and purification of the component enzymes.
The β-crystal formed in PP/PET fiber composites was investigated. The results indicate that PET fibers (PF) can preferably lead to α-crystal formation on their surface. Besides, α-crystals occur earlier than those in the bulk. The β-crystal, might be induced by temperature gradient, only formed away from the PF in composites with lower content of PF. The higher the content of PF is, more possible the PF network is constructed. The transcrystallinity induced by PF will rapidly occupy the region between the adjacent PFs. Consequently, owing to the spatial confinement, β-form is suppressed in the composites with higher content of PF. 相似文献
Composite material film composed of Poly-L-lactic acid (PLLA) and β-tricalcium phosphate (β-TCP) was prepared by a solvent evaporation technique. Cellular cultivation in vitro, Von Kossa staining and MTT assay were performed. The results of cytotoxicity test show that cells cultured in extracts of PLLA/β-TCP and on the surface of composite showed normal growth and proliferation, mineralization nodules were observed for fibroblasts cultured in PLLA/β-TCP extract at day 7. Compared with pure PLLA materials, β-TCP in the PLLA composite facilitate both adhesion and proliferation of rat fibroblasts on the PLLA/β-TCP composite film. 相似文献
The paper deals with the study of some polymer-biologically active principle systems characterized by the controlled release of the bioactive component by hydrolyze followed by diffusion. The systems were obtained by coupling the 2-mercapto-benzotiazolyl-acetic acid and N-(m-nitrobenzoyl)-L-methionine on poly(vinyl alcohol) by means of esteric bonds in the presence of diciclohexylcarbodiimide as an activator. The influence of some coupling process parameters on the reaction efficiency was studied, such as the drug/support and activator/support ratios. The coupling products with a maximum content of biologically active compound were characterized by spectral measurements, also as regards the capacity of bioactive compound release under the conditions simulating those within the gastro-intestinal tract. The antibacterial activity of the conjugates against Staphylococcus aureus, Eschrichia coli, Sarcina lutea, and Bacillus subtilis was determined. 相似文献