Philip C. Bulman Page

Efficient regioselective a-ring functionalization of oestrogens

Abstract Complete series of 2-halo- and 2-cyano-oestrogens have been prepared in good to high yields: 2-chloro, 2-bromo, 2-iodo, and 2-cyano derivatives via oestrogen-thallium (III) bis(trifluoroacetate) intermediates, and 2- and 4- fluorooestrogens by direct functionalization using N -fluoropyridinium triflate.

Enantioselective preparation of 2-substituted- 1,3-dithiane 1-oxides using modified sharpless sulphoxidation procedures

Abstract Enantioselective sulphoxidation of a wide range of 2-substituted-1,3-dithianes has been carried out using modified Sharpless conditions to furnish the corresponding sulphoxides in optically enriched form. Deacylation of 2-acyl-1,3-dithiane 1-oxide derivatives allows the preparation of 2-alkyl-1,3-dithiane 1-oxides and the parent 1,3-dithiane 1-oxide itself in high enantiomeric excesses.

Carbon—sulphur bond formation catalysed by bis(diphenylphosphino)-methane complexes of platinum (II)

Abstract Thiols react with alkyl halides in the presence of sodium carbonate and a catalytic quantity of (dppm)PtCl 2 to give thioethers. Of especial interest is the successful application to thioacetal formation using 1,1-dihalides, which does not require the use of strong bases or the intermediacy of thiolate anions.

A new system for catalytic asymmetric oxidation of sulfides using a hydrogen peroxide based reagent

Abstract Catalytic asymmetric oxidation of sulfides is achieved in a remarkably simple process by treatment with hydrogen peroxide and an enantiomerically pure sulfonylimine under basic conditions.

Asymmetric sulfoxidation using [(3,3-Dimethoxycamphoryl)sulfonyl]oxaziridine

Abstract [(3,3-Dimethoxycamphoryl)sulfonyl]oxaziridine oxidizes sulfides to sulfoxides cleanly and efficiently in up to 98% ee.

A simple and general synthesis of α-keto esters

Abstract α-Keto esters may be prepared directly in good yields by the osmium tetroxide catalysed oxidation of trimethylsilyl acetylenes.

A Simple and Convenient Method for the Oxidation of Sulphides

Abstract Sulphides are efficiently oxidized to either sulphoxides or sulphones as required by treatment with acetonitrile/hydrogen peroxide and potassium carbonate in methanolic solution.

Stereospecific synthesis of exo- and endo-1,3-dimethyl-2,9-dioxabicyclo-[3.3.1]-nonane

Abstract The title compounds may be synthesised in an enantioselective and diastereospecific manner from (±)-4-hydroxynona-2,8-diene using the Sharpless asymmetric epoxidation as the key step in the reaction sequence.

Enantioselective synthesis of (R)-(-)-2,6-dimethyl heptanoic acid:the first application of the DITOX asymmetric building block

Abstract The 1,3-dithiane 1-oxide (DITOX) asymmetric building block/chiral auxiliary has been used to prepare (R)-(−)-2,6-dimethyl heptanoic acid (1), a simple derivative of citronellal, in two steps from (2).

Diastereoselectivity in the addition of Grignard reagents to ketones controlled by the 1,3-dithiane 1-oxide asymmetric building block

Abstract 2-Acyl-1,3-dithiane 1-oxides undergo diastereoselective addition of Grignard reagents; the degree of selectivity observed is highly dependent upon the solvent and the halide counter-ion used; very high selectivities have been observed under certain reaction conditions.