Cu-SSZ-39 zeolite nanosheets-heterogeneous catalyst for the decarboxylative cross-coupling of cinnamic acids with ethers

Mono- or dideprotonation at the N-H groups of the Noyori ketone hydrogenation catalyst trans-[RuH2((R)-BINAP)((R,R)-dpen)] (1a) yields trans-M[RuH2((R,R)-HNCH(Ph)CH(Ph)NH2)((R)-BINAP)], where M = K(+)(8-K) or Li(+) (8-Li), or trans-M2[RuH2((R,R)-HNCH(Ph)CH(Ph)NH)((R)-BINAP)], where M = Li(+) (8-M'2), which have unprecedented activity toward the hydrogenation of amide and imide carbonyls at low temperatures in THF-d8. Details of the origins of the enantioselection for the desymmetrization of meso-cyclic imides by hydrogenation with 8-K are also described herein.

We report the synthesis of Ru(II) and Os(II) trans hydrido-hydroxo complexes by reacting the unsaturated amido complexes MH(NHCMe2CMe2NH2)(PPh3)2 (M = Ru, Os) with stoichiometric amounts of water. Proton exchange is rapid at room temperature between the amine/water/hydroxide moieties which leads to signal averaging of the NMR properties which can be slowed at low temperature in order to see resonances of separate complexes. These compounds can also be cleanly converted back to their starting complexes by dehydration in the presence of 3 Å molecular sieves. X-ray crystal structures of these Ru(II) and Os(II) trans hydrido-hydroxo complexes reveal that the unit cell contains an additional molecule of water trapped in the crystal lattice which hydrogen bonds with a neighbouring hydroxo ligand, forming a water bridged dimer in the solid state. Although there are many cases of oxidative addition of water to transition metal complexes, relatively few cases are well characterized where water addition occurs via metal-ligand cooperation (bifunctional addition) without altering the oxidation state of the metal center.

The transition state for the metal-ligand bifunctional addition step in Noyori's enantioselective ketone hydrogenation was investigated using intramolecular trapping experiments. The bifunctional addition between the Ru dihydride trans-[Ru((R)-BINAP)(H)(2)((R,R)-dpen)] and the hydroxy ketone 4-HOCH(2)C(6)H(4)(CO)CH(3) at -80 °C exclusively formed the corresponding secondary ruthenium alkoxide trans-[Ru((R)-BINAP)(H)(4-HOCH(2)C(6)H(4)CH(CH(3))O)((R,R)-dpen)]. Combined with the results of control experiments, this observation provides strong evidence for the formation of a partial Ru-O bond in the transition state.

The bifunctional addition of lactones/esters is unexpectedly facile at low temperatures. Catalytic hydrogenations of esters can be carried out under mild conditions, e.g. −20 °C under 4 atm of H2, but product inhibition slows these reactions over time.

The catalytic intermediate trans-[Ru((R)-BINAP)(H)2((R,R)-dpen)] (1) reacted on mixing with acetophenone in THF at -80 degrees C under approximately 2 atm H2 to generate the alkoxide trans-Ru((R)-BINAP)(H)((Ph)(Me)CHO)((R,R)-dpen) (6). Contrary to expectations, free Ru-amide and 1-phenylethanol were not the immediate products of this addition reaction. The addition reaction was reversible in THF. 2-Propanol prevents racemization of the alcohol product in THF solvent.

Polymerizations of methyl methacrylate (MMA) and styrene (St) in the presence of bifunctional addition fragmentation chain transfer (AFCT) agents consisting of two α-(alkylthiomethyl)acryloyloxy groups connected by an alkylene group are presented. The moieties from the transfer agent were introduced almost quantitatively at both ends and at the middle of PMMA under appropriate conditions. It was confirmed by NMR spectroscopy that unsaturated and seven-membered cyclic end groups are formed by conventional AFCT and intramolecular cyclization of the radical from the transfer agents. However, formation of the cyclic end groups could be suppressed by structural modification of the transfer agent. PMMA bearing the unsaturated end group at one or both chain ends was employed as a precursor for branched block copolymer preparation.

Abstract As psoralen and other furocoumarin derivatives, intercalated between two base pairs of native DNA, under irradiation at 365 nm form inter-strand cross-linkings as a consequence of bifunctional addition, the writers have investigated the ability of psoralen to give such bifunctional photo­ additions, too, with nucleic acids with disordered or partilly disordered structure (denatured DNA and r-RNA). On the basis of fluorimetric, light-scattering, viscosimetric measurements and of the renaturation ability of denatured bacterial DNA, certain results have been obtained. In addition to monofunctional photoadditions, psoralen can give bifunctional binding by irradiation at 365 nm both with denatured DNA and with r-RNA. However, when irradiation of denatured DNA in the presence of psoralen was performed in a concentrated solution (0.4%), the formation of bifunctional additions between two different strands was demonstrated by the increase (50%) of molecular weight of denatured DNA. However, when irradiation of denatured DNA was performed in more dilute solutions (0.1%), the bifunctional photoaddition of psoralen took place producing only bi­ functional additions in the same strand, very probably with the formation of loops, as has been shown by the absence of increase of molecular weight of DNA and by the more restricted structure assumed by the macromolecule, revealed by the light-scattering and viscosimetric measurements. The formation of these bifunctional additions was confirmed by the reduced rate of renaturation shown by denatured bacterial DNA after irradiation in the presence of psoralen. In the case of r-RNA, psoralen, when irradiated can form bifunctional additions only in the same strand.