Arbuzov rearrangement in the 1,3,2-oxazaphosphinane series

Reactions of 2-alkoxy-1,3,2-oxazaphosphinanes (including 3-alkyl derivatives) with methyl and ethyl bromoacetates give two types of Arbuzov rearrangement products (cyclic and acyclic ones). The ratio between their yields is virtually independent of the nature of the substituent in position 3 of the starting reagent, being mainly determined by the nature of the substituent in the phosphorus bound alkoxy group and varying from 96 : 4 to 2 : 98. Acyclic products can be converted into cyclic ones.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1915–1918, September, 2004.     

Synthesis of alkyl (α-phenylthioalkenyl) ketones containing a (Z)-trisubstituted olefinic fragment

Warren"s method, which has been proposed for the synthesis of -phenylthiodialkyl ketones, appeared to be inefficient for the preparation of their alkenyl alkyl analogs. The latter were prepared in good yields by alkenylation of alkyl phenylthiomethyl ketones with alkenyl bromides.     

Synthesis of a tin-functionalized cyclopentadiene derivative

A 3-tert-butyl-1-(stannylpropyl)-functionalized cyclopentadienyl ligand precursor 6 is readily available in 64% overall yield from allylic alcohol 1 by a three-step reaction sequence including Pd-catalyzed hydrostannylation with Ph₃SnH. Treatment with FeCl₂ and ZrCl₄ · 2THF afforded corresponding ferrocene and zirconocene derivatives. Transmetallation of Sn-Ph with Li-Bu was observed under these reaction conditions by using BuLi as a base.     

Enzymatic synthesis of oligosaccharides, alkyl and terpenyl glucosides, by recombinant Escherichia coli-expressed Pichia etchellsii β-glucosidase II

The biosynthetic activity of yeast Pichia etchellsii β-glucosidase II (BglII) expressed in recombinant Escherichia coli was utilized for synthesis of cellooligosaccharides, alkyl and terpene glucosides. Cellooligosaccharides with a degree of polymerization of 3 and greater were resolved by thin-layer chromatography (TLC) using an ethyl acetate: 1-propanol:2-propanol:water (8:5:1:1) solvent system followed by visualization with 0.2% naphthoresorcinol reagent. Using 2M cellobiose and 15 IU of partially purified BglII, 57 mmol/L of oligosaccharides (comprising mostly cellotriose and cellopentaose) was synthesized in 16 h. Similarly, alkyl glucosides with chain lengths from 6 to 10 carbons were synthesized and products extracted to near purity by ethylacetate extraction. The same extraction method was employed to separate, to near purity, various monoterpenyl (nerol, geraniol, citronellol) glucosides. A reliable and simple method for separation of cellooligosaccharides using a combination of Bio-Gel P-2 gel filtration and charcoal celite adsorption chromatography was developed. The cellooligosaccharides were separated to purity as confirmed by TLC. The enzyme was among the very few that could synthesize a wide variety of glycoconjugates.     

Asymmetric reduction of acetophenone and propiophenone by NaAl(IPTOLate)H2 combined with enantiomeric enrichment of the reaction product as an inclusion complex with IPTOL

An improved procedure was developed for asymmetric reduction of acetophenone and propiophenone by the chiral reagent NaAl(IPTOLate)H₂. This procedure is based on isolation of the chiral alcohol that formed as a crystalline host—guest complex with the IPTOL ligand. The enantiomeric enrichment of the product was as high as 97% ee. The ability of IPTOL and its analogs to form host—guest complexes with a number of ether-type solvents, 1-phenylethanol, and 1-phenylpropan-1-ol as well as thermal stabilities of IPTOL-containing complexes with these alcohols were studied.     

Quaternary Derivatives of α- and β-Scopodonnines and Their Pharmacologic Activity

Several quaternary alkyl halides were synthesized from dimeric tropane alkaloids - and -scopodonnines, which were prepared by dimerization of hyoscine. Their pharmacologic activities were studied.     

Electrocatalytic reduction of alkyl iodides in tetrahydrofuran at silver electrodes

Recent interest in the electrocatalytic activity of silver towards the reduction of alkyl iodides has led us to investigate whether the effect is observed in tetrahydrofuran (THF) at room temperature. Using platinum electrodes in THF for the reduction of alkyl halides at 298 K has been hampered by the solvent window, which ‘obscures’ the voltammetric signals of interest. In order to overcome these problems, voltammetry has been performed at low temperature and was shown to extend the voltammetric window, leading to accurate electrochemical analyses and even novel changes in mechanism(s) of the reactive species following electron‐transfer (ET). Herein, it is shown that for a primary and tertiary alkyl iodide in THF, electroreduction at silver leads to a significant shift in the reduction potential to more positive values compared to platinum. In addition, following reduction, a characteristic series of oxidation peaks are observed and are shown to be due to the specific activity of iodide ions towards silver following reductive cleavage of the parent alkyl iodide. This characteristic feature is not observed with other halide ions: bromide and chloride. Preparative electrolyses at controlled‐potential have suggested that the reduction of the above alkyl iodides is a one‐electron concerted process. The ‘free’ iodide ions act as a monitor of reaction progression, and the carbon‐centred radical either dimerises and/or abstracts a hydrogen atom from the electrolyte/solvent; 1‐iodoadamantane giving percentage yields of 58% adamantane and 39% 1,1'‐biadamantane, the primary alkyl iodide, prepared in‐house, giving 67% R‐H and 25% R‐R. Copyright © 2007 John Wiley & Sons, Ltd.     

Synthesis of low grafting density molecular brush from a poly(N‐alkyl urea peptoid) backbone

The synthesis of a molecular brush was accomplished by combining step‐growth polymerization and reversible addition fragmentation chain transfer (RAFT) polymerization in a “grafting from” methodology. A symmetrical N‐alkyl urea peptoid sixmer containing alkyne functional groups was prepared using a divergent strategy, and the structure of the product was confirmed using NMR spectroscopy and mass spectrometry. A step‐growth process was used to prepare a linear poly(N‐alkyl urea peptoid) by reacting the diamine‐functionalized N‐alkyl urea peptoid sixmer with a diisocyanate. RAFT chain transfer agents were coupled to the poly(N‐alkyl urea peptoid) backbone through a copper‐catalyzed azide/alkyne cycloaddition reaction. The afforded macro‐RAFT agent was used to sequentially polymerize styrene and tert‐butyl acrylate block copolymer arms from the poly(N‐alkyl urea peptoid) backbone. The tert‐butyl groups were removed using dilute trifluoroacetic acid affording hydrophilic polyacrylic acid segments. The molecular brushes were observed to generate micelles in aqueous solution. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011