Journal of Chemical Research

A number of 7-ω-carboxamidoalkyl-substituted estra-1,3,5(10),6-tetraenes as potential ligands for the estrogen receptor ERα have been prepared using either a conjugate addition of α,ω-iodoalkanenitriles or a Michael addition to steroidal ketone 3 as the key step.

A comparison of regioselective (solid sodium alkoxide/toluene) and standard (alcoholic alkoxide solution) alkoxydehalogenation reactions with a series of 2,4-dichloroquinolines and with 2,6-dichloropyridine and 2,4-dichloronitrobenzene, with product analysis by NMR spectroscopy, is reported.

Thieno[2,3-d]pyrimidines have been synthesized by a novel route via thieno[2,3-d]oxazinones which were in turn prepared by a facile single pot method.

Ethyl (E)- and (Z)-3-aryl-3-chloro-2-cyanopropenoates react stereoselectively with 1,2-diamines at room temperature to give ethyl (Z)-3-(2-aminophenylamino)-3-aryl-2-cyanopropenoates, whereas at higher temperatures cyclisation takes place and imidazoles and imidazolines are formed in moderate to high yields.

The reaction of 2-chloro-1-azaazulene (1a) with the benzyne prepared from (phenyl)[o-(trimethyl-silyl)phenyl]iodonium triflate with tetrabutylammonium fluoride gave 1-phenyl-1-azaazulen-2(1H)-one and 8-[2-(2-chloro-1-azaazulen-6-yl)phenyl]-1-azaazulen-2(1H)-one (5), whereas the reaction of 1a with the benzyne prepared from benzenediazonium-2-carboxylate gave 6,10b-etheno-1-azabenz[e]azulen-2(3H)-one (11) together with 12.

Quenching of lithiated isoindolin-1-ones with benzaldehyde gives rise almost exclusively to the erythro (R^*,S^*) adducts.

2-(3-Methylbutoxy)-1,3-benzodithiole has been synthesised in good yield by a modification of the method previously described by Nakayama.

In general, N-aryl-2-chloro-3-oxobutanamides form in solid state an intermolecular hydrogen bond between the anilide hydrogen and the anilide carbonyl oxygen of a neighbouring molecule, which is disrupted in solution. An intramolecular association could not be detected.

A tetrahydrofuran ring can be opened with acyloxyphosphonium bromide generated in situ catalysed by allylsamarium bromide to afford 4-bromobutyl esters under mild conditions in good to excellent yields.

The novel host compounds, (7-isopropyl-1,4a-dimethyl-1,2,3,4,4a,4b,5,6,10,10a-decahydro-phenanthren-1-yl)-diphenyl-methanol (2a) and its p-chlorophenyl- (2b) and p-methoxyphenyl- (2c) derivatives, have been synthesised by the Grignard reaction of abietic acid ethyl ester with the corresponding ArMgBr. The host compounds (2a-2c) include various organic compounds by hydrogen bonding between the host and guest compounds.

Regioselective synthesis of syn-oximes using 3Å molecular sieves under solvent-free condition is described.

An efficient route to a key intermediate in the synthesis of lavendamycin from a suitably substituted 2-chloroquino-line derivative via aminocarbonylation with tryptophan methyl ester as nucleophile, is reported.

The γ-cis effect is identified for the first time in the ¹⁹⁹Hg NMR data presented here, being proposed as a new criterion for the distinction between E and Z isomers of substituted vinylmercury compounds.

The Heck arylation of butyl acrylate and acrylamide with aryl iodides in the presence of catalytic amounts of palladium acetate and tetra-n-butylammonium bromide in pure water using potassium carbonate as base gave the corresponding substituted (E)-butyl cinnamates and (E)-cinnamamides in good yields, respectively.

Photo-oxygenation of racemic phytol has yielded two secondary allylic hydroperoxides and an endoperoxide hemi-acetal, which are the expected products from the “ene-type” reaction of singlet oxygen with the tri-substituted double bond in phytol. Spectral properties for one of the diastereoisomers of phytene-1-ol-2-hydroperoxide obtained from synthesis are shown to be identical with those of a natural product previously reported from Artemisia annua, which, it is concluded, was wrongly assigned as phytene-1,2-diol.

The ¹³C NMR spectra of the bromide of the protonated iminophosphorane -substituted sponge 7 were recorded at different fields. Together with the use of ¹³C satellites of the ³¹P NMR spectrum, these experiments allow determination of a reasonable set of chemical shifts and coupling constants. The most interesting are a ^4hJ_PP = 1.6 Hz, determined directly from the ³¹P NMR spectrum, which probably involves the hydrogen bond, and a ²Δ³¹P(¹³C) isotope shift of 9 ppb.

A general and practical route for the synthesis of dihydropyrimidines by the one-pot cyclocondensation of aldehydes, β-ketoesters and urea is described using NH₂SO₃H as catalyst. Yields and selectivities are significantly better than under classical Biginelli reaction conditions.

Reaction of 2-hydroxy or 2-methoxy substituted benzaldehydes or acetophenones with Meldrum's acid in the presence of a catalytic amount of LiClO₄ or LiBr without solvent under microwave irradiation afforded 3-carboxycoumarins in excellent yields.