Benzylic alcohols and ethers are common subunits in bioactive molecules, as well as useful intermediates in organic chemistry. In this Communication, we describe a new approach to the enantioselective synthesis of benzylic ethers through the chiral phosphine-catalyzed coupling of two readily available partners, γ-aryl-substituted alkynoates and alcohols, under mild conditions. In this process, ...

Sir: We recently reported 1 that cobaloximes and cobalamins reacted with vinyl ethers, in the presence of alcohols, to give aceta Is containing cobalt-carbon cr-bonds. On the basis of these, and earlier 2 experiments, we suggested that the reactions proceeded via the intermediary of a Co(lII)-olefin 7r-complex. Schrauzer, et al.,3 then reported that they were unable to confirm our results and c...

Fluorinated copolymers bearing ammonium groups were prepared by radical copolymerization of fluorinated olefins (chlorotrifluoroethylene, hexafluoropropylene) with different vinyl ethers (2-chloroethyl, cyclohexyl, n-butyl, and ethyl vinyl ethers) followed by the cationization of these copolymers with trimethylamine. Copolymers were obtained in high yield (generally > 85 %), with molecular weig...

A stereoselective and 1,4-benzoquinone-mediated palladium(II)-catalyzed Heck/Suzuki domino reaction involving metal coordinating cyclic methylamino vinyl ethers and a number of electronically diverse arylboronic acids has been developed and studied. Diastereomeric ratios up to 39:1 and 78 % isolated yields were obtained. The stereoselectivity of the reaction was found to be highly dependent on ...

Stabilized AlHCl(2)·(THF)(2) hydroaluminates RC≡CH with exceptional chemo-, regio- and stereoselectivity under efficient ZrCl(2)(η-C(5)Me(5))(2) catalysis (2-5 mol%). The resulting vinyl alanes undergo palladium cross-coupling with a wide range of sp(2) electrophiles (aryl, heteroaryl and vinyl halides/pseudohalides) in good to excellent yields.

Palladium-catalyzed cross-coupling of phenyl, vinyl, and allyl siloxane derivatives proceeded in good to excellent yield with aryl iodides, electron-deficient aryl bromides, and allylic benzoates. Methyl and 2,2,2-trifluoroethyl siloxane derivatives can be employed in the coupling reaction. Electron-donating and -withdrawing groups are tolerated on the aryl halide without affecting the coupling...

Addition of AlMe3 to commercial THF solutions of RZnX (R = aryl, functionalised aryl, vinyl; X = Br, I) simultaneously promotes Schlenk equilibria (leading to competent nucleophiles) and the formation of an Al-Zn-ligand catalyst delivering 80-90% ee for Ar(1)CH(OH)Ar(2) formation from aldehydes.

Rearrangement reactions of cycloalkenyl phenol and naphthyl ethers and the acid-catalyzed cyclization of the resulting product were investigated. Claisen rearrangement afforded 2-substituted phenol and naphthol derivatives. Combined Claisen and Cope rearrangement resulted in the formation of 4-substituted phenol and naphthol derivatives. In the case of cycloocthylphenyl ether the consecutive Cl...

A heterogeneous gold catalyst with remarkable activity for promoting the electrophilic reactions of aryl vinyl ketones and aryl dienyl ketones is described. The catalyst is easy to prepare, is robust, and can be recycled. Low loadings are effective for different types of cationic reactions, including Nazarov cyclizations, lactonizations, and [1,2] shifts.

A palladium complex derived from air-stable TADDOLP(O)H catalyzes efficiently Hiyama, Stille, Kumada and Suzuki cross-coupling reactions of aryl and vinyl chlorides.