Tsutomu Matsuda

Reaction of diazonium salts with transition metals—III: Palladium(0)-catalyzed arylation of unsaturated compounds with arenediazoium salts

Abstract Palladium (0) catalyzed reactions of arenediazonium salts for arylation of aliphatic and cyclic olefins and allylic alcohols, styrene and ethyl acrylate were studied. Effects of the olefinic compounds and other reaction variables on the arylation were presented. Arylpalladium species was proposed as the most plausible intermediated in this reaction.

Reaction of coordinated phosphines—II: Arylation of substituted olefins by palladium(II) acetate and triarylphosphine

Abstract Phenylation of 1-octene, cyclohexene, styrene, acrylonitrile, vinyl acetate, ethyl acrylate, and ethyl but-3-enoate with Pd(PAr 3 ) 2 (OAc) 2 was carried out in acetic acid at 50°. para -Substituted triphenylphosphine palladium acetate complex produced corresponding para substituted phenyl derivatives.

Reaction of diazonium salts with transition metals: IX. Reaction of vinyltrimethylsilane with arenediazonium tetrafluoroborates under palladium(0) catalysis☆

Arenediazonium tetrafluoroborates (ArN2BF4 where ArPh, 4-MeC6H4, 4-BrC6H4, 4-IC6H4 and 4-NO2C6H4) reacted easily with CH2CHSiMe3 at 25 δC to give ArCHCH2, (E-ArCHCHSiMe3 and Ar(Me3Si)CCH2 in excellent yields under palladium(O) catalysis. (E)-ArCHCHSiMe3 compounds were obtained predominantly and isolated in good yields by using an excess of CH2CHSiMe3 over ArN2BF4. Protodesilylation of the reaction mixture afforded styrene derivatives.

Reaction of diazonium salts with transition metals: X. Formylation of arenediazonium salts with carbon monoxide and silyl hydrides under palladium catalysis

Abstract Arenediazonium tetrafluoroborates (ArN 2 BF 4 where Ar = X-C 6 H 4 ; X = H, 2-Me, 3-Me, 4-Me, 4-MeO, 4-MeCO, 4-EtOCO, 2-Ph, 2-Cl, 3-Cl, 4-Cl, 4-Br, 4-I, 3-NO 2 and 4-NO 2 ) were easily converted to aromatic aldehydes (ArCHO) in good yields through the palladium-catalyzed reaction with CO and Et 3 SiH or polymethylhydrosiloxane (PMHS) at room temperature.

Reaction of coordinated phosphines. VI. Divalent palladium promoted cleavage of carbon-phosphorus bonds in tertiary phosphines

Abstract The important role of divalent palladium in the cleavage of carbon—phosphorus bond of tertiary phosphines is revealed by the study of the phenylation in the Pd(OAc) 2 Ph 3 P-styrene system under various conditions; reaction atmosphere, ratio of Ph 3 P/Pd(OAc) 2 , and addition of ethanol or Cu II (OAc) 2 · H 2 O.

Crown–metal interactions in cholesteric liquid crystals

Alkali metal cations bound to steroidal crown ethers can change the helical pitch of cholesteric liquid crystals; the results indicate a potential to apply the liquid crystal as a new host–guest sensory system.

Oxidation of isobutene and methylenecycloalkanes by palladium(II) acetate

Abstract Reactions of isobutene, methylenecyclopentane, methylenecyclohexane and methylenecycloheptane with palladium acetate were studied in acetic acid at 30 to 80°. Two types of oxidation were identified: acetoxylation to allylic acetates (methylenecycloheptane) and oxidative coupling to dimers (isobutene and methylenecyclohexane). A mechanistic study indicated that the former was produced by thermal decomposition of the initially formed π-allylic complex. The latter process was presumed to proceed via an insertion of the olefin into the carbonpalladium bond in the acetoxypalladate adduct, followed by the elimination of the elements of acetic acid and palladium hydride.

Selective extraction and transport of UO22+ with calixarene-based uranophiles

Hexacarboxylate derivatives of p-t-butylcalix[6]arene (2b) and p-hexylcalix[6]arene (3b) extract uranyl ion (UO22+) efficiently and selectively from water into organic media. This high selectivity can be attributed to the nature of calix[6]arene; this is suitably structured for the binding of UO22+, which requires a pseudo-planar hexaco-ordination. When trioctylmethylammonium cation (TMA+) is added to the organic phase, the stoicheiometry of the extraction species [UO22+/(2b)] changes from 1:3 to 1:1–2. This implies that an additional 1–2 mol of UO22+ are adsorbed to (2b) to form ‘neutral’ extraction species and can be displaced by added TMA+. UO22+ is transported by (2b) across a liquid membrane from a neutral IN (source) aqueous phase (pH 8.5) to an acidic OUT (receiving) aqueous phase (0.1 mol dm–3 HCl) in an active transport manner. The rate-determining step is the release of UO22+ from the membrane to the OUT aqueous phase. On the basis of these basic data, we have prepared polymer/liquid-crystal (N-4′-ethoxybenzylidene-4-butylaniline, EBBA/TMA+Cl–) composite membranes immobilising (2b) and have found that the rate of UO22+ transport is efficiently controlled by the changes in pH and temperature. These are novel examples for the selective transport of UO22+.

Formation of calixarene monolayers which selectively respond to metal ions

Calixarene esters show monolayer behaviour characteristic of their ring size; binding of alkali metal ions to the monolayer is specific.

Reaction of diazonium salts with transition metals. XII. Palladium-catalyzed aryldestannylation of α-styrylstannanes by arenediazonium salts

Abstract Under palladium(0) catalysis, Ph(R 3 Sn)CCH 2 (R = Me, Et and Bu) easily reacted with ArN 2 BF 4 (Ar = XPh, X = H, 4-Me, 4-I, 4-MeCO, 4-EtOCO, 3-NO 2 and 4-NO 2 ) and selectively produced ( Z )-PhCHCHAr but not Ph(Ar)CCH 2 . An addition-elimination mechanism instead of the transmetallation from tin to palladium is postulated for this unusual regiochemistry.