Sulphide as a leaving group: highly stereoselective bromination of alkyl phenyl sulphides.

A conceptionally novel nucleophilic substitution approach to synthetically important alkyl bromides is presented. Using molecular bromine (Br), readily available secondary benzyl and tertiary alkyl phenyl sulphides are converted into the corresponding bromides under exceptionally mild, acid- and base-free reaction conditions. This simple transformation allows the isolation of elimination sensitive benzylic β-bromo carbonyl and nitrile compounds in mostly high yields and purities.

Desulfurative Chlorination of Alkyl Phenyl Sulfides.

The chlorination of readily available secondary and tertiary alkyl phenyl sulfides using (dichloroiodo)benzene (PhICl) is reported. This mild and rapid nucleophilic chlorination is extended to sulfa-Michael derived sulfides, affording elimination-sensitive β-chloro carbonyl and nitro compounds in good yields. The chlorination of enantioenriched benzylic sulfides to the corresponding inverted chlorides proceeds with high stereospecificity, thus providing a formal entry into enantioenriched chloro-Michael adducts.

Asymmetric Kita spirolactonisation catalysed by anti-dimethanoanthracene-based iodoarenes.

Enantiopure C2-symmetric iodoarenes based on the rigid all-carbon anti-dimethanoanthracene framework are shown to catalyse the asymmetric oxidative Kita spirolactonisation of propanoic acid-tethered 1-naphthols with significant levels of asymmetric induction of up to 67% ee.

Unified strategy for iodine(III)-mediated halogenation and azidation of 1,3-dicarbonyl compounds.

A mild and rapid (diacetoxyiodo)benzene-mediated formal electrophilic α-azidation of 1,3-dicarbonyl compounds using commercially available Bu4NN3 as the azide source is reported. The reaction conditions employed are based on optimization studies conducted on the analogous halogenations with Et4NX (X = Cl, Br, I).

The first asymmetric ring-expansion carbonylation of meso-epoxides.

The first asymmetric ring-expansion carbonylation of meso-epoxides to β-lactones is reported. Two structurally diverse chiral Cr(III) chloro complexes in conjunction with Co(2)(CO)(8) were shown to be competent catalytic systems for this transformation, displaying significant levels of asymmetric induction of up to 56% ee.

Congested C2-symmetric aryliodanes based on an anti-dimethanoanthracene backbone.

A family of congested aryliodanes based on an anti-dimethanoanthracene backbone has been synthesised and two diaryliodonium salts and the iodyl derivative characterised by X-ray analysis. The latter shows a rare water coordination to the iodine(V) centre in the solid state. Applications of these reagents in functional group transfer reactions are reported.

Deoxygenation of hydroquinones as a general route to norbornane-fused aromatic systems: an entry into substituted and functionalized dimethano- and methanoanthracenes.

A high-yielding route to substituted and functionalized dimethanoanthracenes by the Pd-catalyzed deoxyenation of the corresponding hydroquinone precursors is described. Attempts were made to deoxygenate the 9,10-dimesylate, ditosylate, and ditriflate derivatives of anti-dimethanoanthracene 1a, and it was found that under the studied conditions only the ditriflate 8a gave the corresponding deoxygenated aromatic scaffold. Optimization of the reaction conditions identified the Pd(OAc)(2)/dppf tandem as a suitable catalytic system for this transformation.

In situ generation of the Coates catalyst: a practical and versatile catalytic system for the carbonylation of meso-epoxides.

A highly active catalytic system for the carbonylation of meso- and terminal epoxides to β-lactones is described. The active catalyst, analogous to Coates' catalyst, is generated in situ from commercially available (TPP)CrCl and Co(2)(CO)(8). This practical system circumvents the preparation of air sensitive cobaltate salts, operates at low catalyst loadings, and allows the carbonylation of functionalized, sterically demanding and heterocyclic meso-epoxides.

Umpolung of halide reactivity: efficient (diacetoxyiodo)benzene-mediated electrophilic alpha-halogenation of 1,3-dicarbonyl compounds.

An efficient high-yielding (diacetoxyiodo)benzene-mediated alpha-halogenation of 1,3-dicarbonyl compounds utilising titanium tetrahalides as the halide source has been developed.

Intermolecular interactions in (arene)chromium carbonyl compounds: prediction of chiral crystal packing from racemate structure.

Six X-ray crystal structures are reported, all containing substituted triphenylmethanol derivative 4 either alone or as its mono or bis(chromium tricarbonyl) complexes. All four chromium complexes studied crystallize with two independent molecules in the crystallographic asymmetric unit. It is demonstrated that from the X-ray crystal structure of the acentric racemic (+/-)-(1pR,1' 'R)(1pS,1' 'S)-[Cr(CO)(3)(eta(6)-t-BuC(6)H(3)(CMeOMe)CPh(2)OH)], (+/-)-3, it is possible to deduce the 4-fold helical structure of the chiral (-)-(1pR,1' 'R) isomer, (-)-3.

Phosphoramidate-mediated conversion of carbonyl ligands into isocyanide ligands: a new approach to chiral isocyanide ligands.

Metal isocyanides have been used and studied by organometallic chemists for many years and, as a result, they have a rich and interesting chemistry. The nature of metal-free isocyanides and the methods of making isocyanide complexes, however, has resulted in the vast majority of studies to date being performed with structurally simple isocyanides. We report here a new approach to the synthesis of isocyanide ligands that involves the reaction of a metal carbonyl ligand with the anion of a phosphoramidate.