Solvolytic behavior of p-dimethylamino-α-bromostyrene in water solutions

Nmr and UV studies show that $\text{p}$-dimethylamino-$\text{α}$-bromostyrene, I, undergoes S_Nl reaction in H₂O and HClO₄ (^kS_Nl = 6 × 10^?1sec.^?1 at 25°). The vinyl cation has an extraordinary selectivity for capture by aromatic amines relative to H₂O, including I itself to give the dimer II.     

Behavior of p-dimethylamino-α-bormostyrene and its dimer in dioxane-water

Monomeric $\text{p}$-dimethylamino-$\text{α}$-bromostyrene undergoes S_Nl increasingly slowly in 60 to 91% dioxane. Reaction is catalyzed by HClO₄, NaOH and NaClO₄. Dimer 11 reverts to monomer I in 91% dioxane. There is only a small solvent effect on the solvolysis rate of II.     

Total synthesis of (+--oudemansin

($\text{+}\text{-}$)-Oudemansin has been synthesized starting from $\text{trans}$-cinnamaldehyde by a route involving the stereoselective Zn(BH₄)₂ reduction of β-keto ester.     

Stereocontrolled (E,Z and erythro, threo) synthesis of ⊙-hydroxyallylic sulphides

All four isomers of substituted 3-alkylthio-4-hydroxybutenes have been synthesised: both the geometry of the double bond and the relative stereochemistry of the two chiral centres are controlled.     

The ipso-nitration of p-cresol

The nitration of $\text{p}$-cresol by nitric acid in aqueous sulphuric acid involves ~40% $\text{ipso}$-substitution at C^Me. The 4-methyl-4-nitrocyclohexa-2,5-dien-1-one (I) formed undergoes an acid-catalysed rearrangement to 4-methyl-2-nitrophenol.     

Advanced sedex (sensitive detector of exothermic processes)

The instrument described is suitable for the investigation of the thermal behaviour of substances and reaction mixtures under production conformable conditions; this is made possible by the sophisticated design of the sample chamber: easy stirring of the samples, measuring under any gas atmosphere and while bubbling gas through the sample, choice of the sample container and visual observation during the measurement. The control device allows the choice of one of three operational modes: constant temperature, linear increase in temperature, and adiabatic control; this permits the application of the SEDEX apparatus for a variety of methods including dynamic scanning, isoperibolic measurements, and (quasi) adiabatic studies.     

[2+2] Cycloaddition of benzyne to cis,trans- and cis,cis-1,5-cyclooctadiene

The relative rates of formation of $\text{cis}$ and $\text{trans}$ [2+2]cycloadducts of benzyne to $\text{cis}$, $\text{trans}$- and $\text{cis}$, $\text{cis}$-1,5-cyclooctadiene, $\text{trans}$- and $\text{cis}$-cyclooctene are discussed and properties of the adducts (e.g., their unusual hydrogenation) are described.     

A total synthesis of (+)-anhydrocannabisativine.

Racemic anhydrocannabisativine has been efficiently synthesized by employing a β -lactam-imino ether coupling reaction. The key to the formation of the tetrahydropyridine moiety of the natural alkaloid is a stereoselective intramolecular conjugate addition of a secondary amino group to a $\text{Z}$,$\text{E}$ dienone.     

Diastereoselective synthesis of N-acetyl-D,L-acosamine and N-benzoyl-D,L-ristosamine

N-Acyl derivatives of $\text{D}$,$\text{L}$-acosamine and $\text{D}$,$\text{L}$-ristosamine were synthesized with high stereo selectivity utilizing intramolecular Michael addition of γ- and δ-carbomoyloxy-α,β-unsaturated esters.     

The unexpected intramolecular C-arylation of 2-0-benzylated cyclic sugar derivatives: a useful 1,2-cis-C-glycosylation reaction

Upon treatment with tin(IV) chloride, perbenzylated glycofuranosyl acetates such as 3 or 6 undergo an unusual, intramolecular α-$\text{C}$-arylation resulting from the internal Friedel-Crafts alkylation of the 2-$\text{O}$-benzyl substituent.     

Stereoselective photosolvolyses of ipso-acetoxynitro-adducts of p-xylene

Diastereoisomers of 1,4-dimethyl-4-nitro-2,5-cyclohexadienyl acetate exchanged acetoxyls for alkoxyls on irradiation in alcohols to give the diastereoisomers of alkyl, 1,4-dimethyl-4-nitro-2,5-cyclohexadienyl ethers in isomer ratios of 70:30, whereas the irradiation in pentane yielded $\text{p}$-xylene.     

MIRC (Michael Initiated Ring Closure) Reactions Formation of Three,Five, Six and Seven Membered Rings

The term MIRC reaction is defined. Examples of the construction of three, five, six and seven membered rings using alkylthiolates and LDA as nucleophiles are presented.