Ruthenium hydride fluoride

A ruthenium hydride fluoride, [RuHF(CO)L2] (L = P Bu2Me) has also figured in new chemistry of CF2 as a ligand [54], The complex was prepared by reaction of [RuHCl(CO)L2] and anhydrous CsF in acetone. Compounds of the same general formula have also been used in detailed studies on reactivity and stereochemistry of ligands attached to ruthenium centres. Thus, the relative electron-donating ability... 

The diols (97) from asymmetric dil droxylation are easily converted to cyclic sii e esters (98) and thence to cyclic sulfate esters (99).This two-step process, reaction of the diol (97) with thionyl chloride followed by ruthenium tetroxide catalyzed oxidation, can be done in one pot if desired and transforms the relatively unreactive diol into an epoxide mimic, ue. the 1,2-cyclic sulfate (99), which is an excellent electrophile. A survey of reactions shows that cyclic sulfates can be opened by hydride, azide, fluoride, thiocyanide, carboxylate and nitrate ions. Benzylmagnesium chloride and thie anion of dimethyl malonate can also be used to open the cyclic sulfates. Opening by a nucleophile leads to formation of an intermediate 3-sidfate aiuon (100) which is easily hydrolyzed to a -hydroxy compound (101). Conditions for cat ytic acid hydrolysis have been developed that allow for selective removal of the sulfate ester in the presence of other acid sensitive groups such as acetals, ketals and silyl ethers. 

BENSULFOID (7704-34-9) Combustible solid (flash point 405°F/207°C). Finely divided dry materia forms explosive mixture with air. The vapor reacts violently with lithium carbide. Reacts violently with many substances, including strong oxidizers, aluminum powders, boron, bromine pentafluoride, bromine trifluoride, calcium hypochlorite, carbides, cesium, chlorates, chlorine dioxide, chlorine trifluoride, chromic acid, chromyl chloride, dichlorine oxide, diethylzinc, fluorine, halogen compounds, hexalithium disilicide, lampblack, lead chlorite, lead dioxide, lithium, powdered nickel, nickel catalysis, red phosphorus, phosphorus trioxide, potassium, potassium chlorite, potassium iodate, potassium peroxoferrate, rubidium acetylide, ruthenium tetraoxide, sodium, sodium chlorite, sodium peroxide, tin, uranium, zinc, zinc(II) nitrate, hexahydrate. Forms heat-, friction-, impact-, and shock-sensitive explosive or pyrophoric mixtures with ammonia, ammonium nitrate, barium bromate, bromates, calcium carbide, charcoal, hydrocarbons, iodates, iodine pentafluoride, iodine penloxide, iron, lead chromate, mercurous oxide, mercury nitrate, mercury oxide, nitryl fluoride, nitrogen dioxide, inorganic perchlorates, potassium bromate, potassium nitride, potassium perchlorate, silver nitrate, sodium hydride, sulfur dichloride. Incompatible with barium carbide, calcium, calcium carbide, calcium phosphide, chromates, chromic acid, chromic... 

Yamauchi et al. completed an ex-chiral pool synthesis of a samin-type lignan, Scheme (38) [102]. The diprotected tetraol 230 was obtained from Z-glutammic acid by a 15 step procedure in 7-8% overall yield [103]. The diprotected tetraol 230 was treated with boron trifluoride diethyl etherate in dichloromethane to give the tetrahydrofuran 231 in 84%-87% yield. After deprotection with tetrabutylammonium fluoride, the resulting diol was oxidized by dihydridotetrakis(triphenylphospine)ruthenium(II) to provide two lactones 232 and 233 in a ratio of 2 1. Lactone 232 was transformed in samin-type lignan 234 by diisobutylaluminium hydride reduction in 70% yield. 

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