Convenient ketone synthesis via n-acylaziridines

N-Acylaziridines couple efficiently with organolithium and Grignard reagents to produce ketones in high yields.     

Synthesis of carbazoles via 2-vinylindoles.

2-Vinylindoles are obtained from the Fischer indolization of α,β-unsaturated ketones. Heating 2-(2-methylpropenyl)indole (4) with the Vilsmeier reagent (DMF/POCl₃) gave 2-methylcarbazole in good yield, presumably $\text{via}$ an electrocyclic ring closure of a hexatrienic intermediate.     

cis Δ5-octahydro-1-naphtalenones and cis Δ5-decahydro-1-naphthalenes (cis-1-decalones) by stereoselective intramolecular diels-alder reaction.

Intramolecular DIELS-ALDER reactions of requisite trienes led to $\text{cis}$-1-decalones, $\text{via}$ an endo intermediate state.     

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.     

Epimerization of bicyclic vinyl tertiary-alcohols via [2,3] sigmatropic rearrangement

General methods for inverting the stereochemisty of vinyl $\text{tertiary}$-alcohols such as $\text{2}$ and $\text{5}$ into $\text{3}$ and $\text{8}$ respectively are described. The procedures employ a [2,3] sulfoxide rearrangement and will facilitate the extended use of the oxy-Cope rearrangement to a variety of related ring systems.     

Preparation of gem-difluorocyclopropanes via decomposition of methyl chlorodifluoroacetate by alkali metal halides

The facile decomposition of methyl chlorodifluoroacetate, induced by either lithium chloride/hexamethylphosphoric triamide complex or potassium fluoride/18-Crown-6 complex, has been carried out in the presence of a variety of olefinic substrates to yield the corresponding $\text{gem}$-difluorocyclopropanes. The ester decomposition has been determined to yield “free” difluorocarbene $\text{via}$ a three-step process involving an intermediate chlorodifluoromethide ion.     

β-tributylstannylacrylates. Stereospecific synthesis via conjugate additon of tributylstaknylcopper

The synthesis of $\text{cis}$- and $\text{trans}$-8-tributylstannylacrylates from conjugate addition of tributylstannylcopper to various β-substituted acrylates is shown to be a highly stereospecific reaction. Of four tributylstannylmetal reagents examined for this conversion, optimum results were obtained with tributylstannylcopper.     

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.     

Photoaddition reactions of trans dichloroethylene with benzenoid compounds: facile formation of tetracyclo[3.3.0.02,804,6]octanes and semibullvalenes

$\text{trans}$ 1,2-Dichloroethylene undergoes a stereospecific photoreaction with benzonitrile, the three tolunitriles, α,α,α-trifluorotoluene, fluorobenzene, and chlorobenzene to give substituted 6-$\text{exo}$ 7-$\text{endo}$ dichlorotricyclo[3,3,0,0_2,8]oct-3-enes which on treatment with base yield cyclised products or semibullvalenes: phenol yields dichlorobicyclo[3.2.1]oct-2-en-8-one with this ethylene photochemically.