anti-Markovnikov product. To account for the high regioselectivity of catalyzed hydroboration, Hayashi proposed a mechanism involving a η3-benzylrhodium complex. Catalyzed hydroboration-oxidation of substituted alkenes can be rendered enantioselective. In 1990, Brown and co-workers achieved asymmetric hydroboration using an achiral catalyst and chiral borane sources derived from ephedrine and pseudoephedrine. In most cases, the regioselectivity was poor although the ee values can be close to 90%. Use of a chiral catalyst and an achiral borane source is more common, e.g. chiral diphosphines such as BINAP. Styrene or its simple derivatives are usually the prochiral substrate. Enantioselectivity tends to be lowered with ortho-substituents on the aromatic ring, as well as further substitution on the olefin. Successful results have also been obtained on other reactants. The second class of ligands is phosphinamine ligands. In 1993, Brown first reported the successful use of QUINAP in asymmetric alkene hydroboration. QUINAP improve upon the intolerance of substitution on the aromatic ring as observed for diphosphine ligands. Reactions using styrene and derivatives with electron-donating groups on the para position still gave high ee values. Similar results were also obtained on cyclic vinyl arenes. Such results expand the scope of asymmetric hydroboration to more sterically demanding alkenes. Several new ligands of this class have also been developed. Some recent results are summarized below. The studies above have all utilized oxidation of the boronate esters to produce alcohols, which is a severe limitation to the synthetic scope of such species, especially when they can be made enantioselectively. Another important class of compounds that can be derived from boronate esters is α-substituted benzylamines, some of which are commercially useful. The synthesis of such chiral amines via catalytic hydroboration involves conversion of the catecholboronate ester to trialkylborane by diethyl zinc or methylmagnesium chloride. Reaction of the trialkylborane with hydroxylamine-O-sulfonic acid produces primary benzylamines. Secondary amines can also be prepared by in situ formation of N-chloramines. References Organometallic chemistry Catalysis