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[Reaction: see text]. The enantioselective synthesis of both enantiomers of tetrahydropalmatine (2) (ee = 98%), a natural alkaloid belonging to the tetrahydroprotoberberine family, is described. The key step of this total synthesis is based on our tandem 1,2-addition/ring-closure methodology employing lithiated methylbenzamide and benzaldehyde SAMP or RAMP hydrazones as substrates. An initial route was investigated for the formation of N- and 3-substituted dihydroisoquinolones starting from 2-substituted benzaldehyde SAMP hydrazones, but although high diastereoselectivity was achieved, only disappointing yields were obtained. In our subsequent synthetic strategy, 2,3-dimethoxy-6-methylbenzamide 6 and 3,4-dimethoxybenzaldehyde SAMP or RAMP hydrazone 19 gave the dihydroisoquinolones 20 in high diastereomeric purity (de > or = 96%) and reasonable yield (54-55%), taking into account the complex functionalities established in one step. Cleavage of the N-N bond of the chiral auxiliary and reduction of the carbonyl group of the amide moiety were performed in the same step, and the resulting tetrahydroisoquinolines 22 (ee = 99%) were N-functionalized by treatment with various electrophiles to investigate the ring closure by Pummerer, Friedel-Crafts, and Pomeranz-Fritsch reactions. The Pummerer cyclization led to the formation of (S)-(-)-2 with slight racemization (ee = 89%), whereas the Friedel-Crafts reaction proved to be unsuccessful. Finally, Pomeranz-Fritsch-type cyclization afforded the desired title compound (R)-(+)-2 in excellent enantioselectivity in 9% overall yield over seven steps and after optimization of the last step (S)-(-)-2 in 17% overall yield. 相似文献
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Lagoja IM Pochet S Boudou V Little R Lescrinier E Rozenski J Herdewijn P 《The Journal of organic chemistry》2003,68(5):1867-1871
The synthesis of fully [13C/15N] labeled pyrimidine nucleosides has been achieved from 13C-glucose and labeled nucleobases. The reaction scheme leads directly to the protected nucleosides without the need for the inversion of configuration of C-3 of 13C-glucose. This was achieved by an oxitative ring-opening reaction removing the carbon with the wrong configuration. 相似文献
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Poupart S Boudou C Peixoto P Massonneau M Renard PY Romieu A 《Organic & biomolecular chemistry》2006,4(22):4165-4177
The synthesis and photophysical properties of a new terpyridine-based europium(III) chelate (Eu (TMT)-AP3) designed for peptide and protein labelling in aqueous solution phase is described. In order to obtain a stable, easy to handle, versatile and efficient labelling agent, a reactive aminopropargyl arm has been introduced onto the terpyridine moiety. As preliminary biochemical applications the chelate has been 1) efficiently covalently attached onto a representative biomolecule-monoclonal antibody-and 2) converted into iodoacetamido and aldehyde derivatives, and the photoluminescent Eu (TMT)-AP3 was grafted onto cysteine and lysine amino acid residues respectively. These two different solution phase labelling methods yielded original fluorogenic FRET based probes suitable for "in vitro" detection of caspase-3 protease, a key mediator of apoptosis of mammalian cells. 相似文献
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We develop a general technique, based on a Bochner-type identity, to estimate spectral gaps of a class of Markov operator. We apply this technique to various interacting particle systems. In particular, we give a simple and short proof of the diffusive scaling of the spectral gap of the Kawasaki model at high temperature. Similar results are derived for Kawasaki-type dynamics in the lattice without exclusion, and in the continuum. New estimates for Glauber-type dynamics are also obtained. 相似文献
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[reaction: see text] A general, efficient, and experimentally simple method for the generation of sulfenate salts has been developed using beta-sulfinylesters as substrates. The process is based on a retro-Michael reaction, initiated by deprotonation at low temperature. Upon treatment with alkyl halides, the liberated sulfenates are subsequently converted into sulfoxides in good to excellent yield. Extension of the methodology to an unprecedented access to nonracemic sulfoxides by introduction of an enantiopure ligand, (-)-sparteine, is also described. 相似文献
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Thomas Crouzier Thomas Boudou Catherine Picart 《Current Opinion in Colloid & Interface Science》2010,15(6):417-426
In recent years, the layer-by-layer technique has grown in various fields. One of the emerging trends of bio-applications is the use of polysaccharides as main film components, which stems from their intrinsic physical, chemical and biological properties. These allow the simple formation, by self-assembly, of new kinds of mimics of extra-cellular matrices from plant and animal tissues. These assemblies, which possess specific properties arising from their hydration and internal composition, can indeed contain additional functionalities obtained by chemical modification of the biopolymers or film post-processing. They can be molded into different forms (films, membranes, and capsules). 相似文献
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C-P cross-coupling reactions between phosphine-borane complexes and aryl iodides are successfully performed in imidazolium based ionic liquids (ILs). To improve the recycling of the catalyst, a monophosphine covalently attached to a pyridinium salt was prepared. Associated to palladium, this catalyst shows a high catalytic activity and stays immobilized in the IL. It was reused at least in six cycles. 相似文献