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1.
Several 2- and 4-alkylcyclohexadienones were prepared and shown to accept electrons to produce ketyl radical anions that dissociated rapidly at room temperature to release carbon-centered radicals and an aromatic phenoxide type anion. In the PET process with benzyl-substituted cyclohexadienones, initiated with triethylamine, the benzyl radicals dimerised or abstracted an H-atom from solvent. In electrochemical reductions, and in reductions with alkali metals in liquid ammonia, the benzyl radicals were further reduced to anions. 相似文献
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3.
Ulrik Gran 《Tetrahedron》2003,59(24):4303-4308
A new macrocyclic NADH model 1 has been designed and synthesised. The new model consists of the same subunits as previously reported models. However, the present model is designed as such that the pyridine nitrogen of the nicotinamide units are not incorporated in the macrocyclic framework. Thus, properties such as solubility can easily be varied by alkylation with an appropriate agent. The macrocyclic framework was prepared in 7 steps. Methylation of the pyridine nitrogens followed by reduction gave the desired model. This model compound was found to reduce methyl benzoylformate stereoselectively in good yield with 48% enantiomeric excess. 相似文献
4.
Anirban Kar 《Tetrahedron》2005,61(22):5297-5302
Starting from citraconic anhydride (13), a simple multistep (9-10 steps) synthesis of naturally occurring butyrolactones maculalactone A (3), maculalactone B (1), maculalactone C (2) and nostoclide I (4) have been described with good overall yields via dibenzylmaleic anhydride (20) and benzylisopropylmaleic anhydride (27). The two anhydrides 20 and 27 were prepared by SN2′ coupling reactions of appropriate Grignard reagents with dimethyl bromomethylfumarate (14), LiOH-induced hydrolysis of esters to acids, bromination of carbon-carbon double bond, in situ dehydration followed by dehydrobromination and chemoselective allylic substitution of bromoatom in disubstituted anhydrides 19 and 26 with appropriate Grignard reagents. The NaBH4 reduction of these anhydrides 20 and 27 furnished the desired lactones 21 and 29, respectively. The lactone 21 on Knoevenagel condensation with benzaldehyde, furnished maculalactone B (1), which on isomerization gave maculalactone C (2). Selective catalytic hydrogenation of 1 gave maculalactone A (3). The conversion of lactone 29 to nostoclide I (4) is known. 相似文献
5.
A stereoselective total synthesis of (S)-Virol C and (S)-1-dehydroxyvirol A has been developed, based upon the selective and sequential substitution of the two trimethylsilyl groups of readily available 1,4-bis(trimethylsilyl)-1,3-butadiyne. 相似文献
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A new, continuous-flow consecutive reduction method was developed for the C-N bond formation in the synthesis of the key intermediate of the antipsychotic drug cariprazine. The two-step procedure consists of a DIBAL-H mediated selective ester reduction conducted in a novel, miniature alternating diameter reactor, followed by reductive amination using catalytic hydrogenation on 5% Pt/C. The connection of the optimized modules was accomplished using an at-line extraction to prevent precipitation of the aluminum salt byproducts. 相似文献
8.
Theodore D. Sideris Panayiotis V. Ioannou 《Phosphorus, sulfur, and silicon and the related elements》2013,188(5):1017-1030
The scope of ascorbic acid/iodine and triphenylphosphine/iodine in methanol for the direct reduction of arsenic(V) compounds having the As[dbnd]O group has been investigated. Ascorbic acid/iodine reduces arsonic acids, diphenylarsinic acid (but not dimethylarsinic acid), and triphenylarsine oxide. The rates of reduction depend on the electronic effects of the ligands bound to arsenic and on the hydrogen-bonding strength of the species, when present. When the As(V) compound has an [sbnd]NH 2 or an [sbnd]NH 3 + group, the reduction product reacts with a ketonic form of dehydroascorbic acid, giving condensation product(s). Triphenylphosphine/iodine reduced slowly the zwitterionic o-aminophenylarsonic acid but reduced faster the hydrochloric acid salt of the same acid. It reduced dimethylarsinic acid as well because the powerful electron-withdrawing Ph 3 P +coordinated to As[dbnd]O seems to outweigh the electronic and hydrogen bonding effects. 相似文献
9.
《Green Chemistry Letters and Reviews》2013,6(1):25-30
Abstract The enzymatic reduction of prochiral heterocyclic ketones by carrot (Daucus carota) root in water afforded the corresponding S-alcohols in accordance with the Prelog's rule. The reaction was performed under various conditions in order to optimize the procedure of bioreduction regarding reaction time, yield, and optimal mass of carrot. The optimized procedure was used to test the ability of other plants to carry out the reaction. In the latter experiment, it was observed that, with regard to stereospecificity, most vegetables tested were poorer reducing agents compared to D. carota. 相似文献
10.
Let (Xn,dn) be a sequence of finite metric spaces of uniformlybounded diameter. An equivalence relation D on the product defined by if and only if is a c0-equality.A systematic study is made of c0-equalities and Borel reductionsbetween them. Necessary and sufficient conditions, expressedin terms of combinatorial properties of metrics dn, are obtainedfor a c0-equality to be effectively reducible to the isomorphismrelation of countable structures. It is proved that every Borelequivalence relation E reducible to a c0-equality D either reducesa c0-equality D' additively reducible to D, or is Borel-reducibleto the equality relation on countable sets of reals. An appropriatelydefined sequence of metrics provides a c0-equality which isa turbulent orbit equivalence relation with no minimum turbulentequivalence relation reducible to it. This answers a questionof Hjorth. It is also shown that, whenever E is an F-equivalencerelation and D is a c0-equality, every Borel equivalence relationreducible to both D and to E has to be essentially countable.2000 Mathematics Subject Classification: 03E15. 相似文献