Cyclopropenes for the Stepwise Synthesis of 1,2,4,5-Tetraarylbenzenes via 1,4-Cyclohexadienes.

This paper describes a synthetic approach to the synthesis of 1,2,4,5-tetraarylbenzene derivatives from cyclopropenes. The Lewis acid-mediated dimerization of cyclopropenes gives tricyclo[3.1.0.02,4]hexane derivatives. The subsequent thermal ring-opening reaction under solvent-free conditions gives 1,4-cyclohexadienes bearing quaternary carbons. The novel Br2-mediated oxidative rearrangement of 1,4-cyclohexadienes takes place to give 1,2,4,5-tetraarylbenzene derivatives in high to excellent yields.

Regio- and Stereoselective Synthesis of Multi-Alkylated Allylic Boronates through Three-Component Coupling Reactions between Allenes, Alkyl Halides, and a Diboron Reagent.

Multisubstituted allylic boronates are attractive and valuable precursors for the rapid and stereoselective construction of densely substituted carbon skeletons. Herein, we report the first synthetic approach for differentially 2,3,3-trialkyl-substituted allylic boronates that contain a stereodefined tetrasubstituted alkene structure. Copper(I)-catalyzed regio- and stereoselective three-component coupling reactions between gem-dialkylallenes, alkyl halides, and a diboron reagent afforded sterically congested allylic boronates. The allylboration of aldehydes diastereoselectively furnished the corresponding homoallylic alcohols that bear a quaternary carbon. A computational study revealed that the selectivity-determining mechanism was correlated to the coordination of a boryl copper(I) species to the allene substrate as well as the borylcupration step.

Copper(I)-Catalyzed Enantioconvergent Borylation of Racemic Benzyl Chlorides Enabled by Quadrant-by-Quadrant Structure Modification of Chiral Bisphosphine Ligands.

The first copper(I)-catalyzed enantioselective borylation of racemic benzyl chlorides has been realized by a quadrant-by-quadrant structure modulation of QuinoxP*-type bisphosphine ligands. This reaction converts racemic mixtures of secondary benzyl chlorides into the corresponding chiral benzylboronates with high enantioselectivity (up to 92 % ee). The results of mechanistic studies suggest the formation of a benzylic radical intermediate. The results of DFT calculations indicate that the optimal bisphosphine-copper(I) catalyst engages in noncovalent interactions that efficiently recognize the radical intermediate, and leads to high levels of enantioselectivity.

Semireduction of Alkynes Using Formic Acid with Reusable Pd-Catalysts.

The treatment of PdCl2 with K2CO3 and HCO2H in dioxane gives black precipitates, which are an effective catalyst for the semireduction of alkynes to alkenes using formic acid as a reductant. Even 0.05 mol % Pd promoted the reduction reaction of tolane in high yield with high selectivity.

Post-Treatment-Free Solution-Processed Reduced Phosphomolybdic Acid Containing Molybdenum Oxide Units for Efficient Hole-Injection Layers in Organic Light-Emitting Devices.

We report the development of solution-processed reduced phosphomolybdic acid (rPMA) containing molybdenum oxide units for post-treatment-free hole-injection layers (HILs) in organic light-emitting devices (OLEDs). The physical and chemical properties of rPMA, including its structure, solubility in several solvents, film surface roughness, work function, and valence states, were investigated. The formation of gap states just below the Fermi level of rPMA was observed. Without any post-treatment after the formation of rPMA films, OLEDs employing rPMA as an HIL exhibited a very low driving voltage and a high luminous efficiency. The low driving voltage was attributed to the energy level alignment between the gap states formed by reduction and the HOMO level of the hole-transport layer material N,N'-bis(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine.

Polyoxometalate-Assisted, One-Pot Synthesis of a Pentakis[(triphenylphosphane)gold]ammonium(2+) Cation Containing Regular Trigonal-Bipyramidal Geometries of Five Bonds to Nitrogen.

Novel intercluster compounds consisting of pentakis[(triphenylphosphane)gold]ammonium(2+) cation (1) and Keggin polyoxometalate (POM) anions, i.e., {[Au(PPh3)]5(µ5-N)}3[α-PM12O40]2 (1-PW for M = W; 1-PMo for M = Mo), were synthesized in 30-36% yield by one-pot reaction of the protonic acid form of the Keggin POMs, H3[α-PM12O40]·nH2O (n = 13 for M = W; n = 15 for M = Mo) with monomeric (triphenylphosphane)gold(I) carboxylate [Au(RS-pyrrld)(PPh3)] [RS-Hpyrrld = (RS)-2-pyrrolidone-5-carboxylic acid] in the presence of aqueous NH3 at a molar ratio of 2:15:x (x = 3 for 1-PW; x = 7.5 for 1-PMo). These compounds resulted from the nitrogen-centered phosphanegold(I) clusterization of in situ generated monomeric phosphanegold(I) units, [Au(PPh3)]+ or [Au(L)(PPh3)]+ (L = NH3 or solvent), during the carboxylate elimination of [Au(RS-pyrrld)(PPh3)] in the presence of the Keggin POMs and aqueous NH3. The products 1-PW and 1-PMo were characterized by elemental analysis, Fourier transform infrared, thermogravimetric and differential thermal analyses (TGA/DTA), X-ray crystallography, and solid-state cross-polarization magic-angle-spinning (CPMAS) (31P and 15N) and solution (31P{1H} and 1H) NMR spectroscopy. The lattice contained three independent {[Au(PPh3)]5(µ5-N)}2+ cations, of which two took regular trigonal-bipyramidal (TBP) geometries and the third took a distorted, square-pyramidal (SP) geometry. These geometries are in contrast to those reported by Schmidbaur's group for {[Au(PPh3)]5(µ5-N)}2+ cations as BF4 salts. Density functional theory and ONIOM calculations for {[(L3P)Au]nN}(n-3)+ (L = H or Ph; n = 4-6) showed that the pentacoordinate cluster is energetically most stable and its TBP structure is only 1.6 kcal mol-1 more stable than its SP structure, in accordance with the experimental facts.

(Z)-Selective Enol Triflation of α-Alkoxyacetoaldehydes: Application to Synthesis of (Z)-Allylic Alcohols via Cross-Coupling Reaction and [1,2]-Wittig Rearrangement.

The stereoselective transformation of α-alkoxyacetoaldehydes to the corresponding (Z)-vinyl triflates was achieved by treatment with phenyl triflimide and DBU. The stereochemistry was explained by the "syn-effect," which was attributed primarily to an σ → π* interaction. The ß-alkoxy vinyl triflates obtained were applied to the stereoselective synthesis of structurally diverse (Z)-allylic alcohols via transition metal-catalyzed cross-coupling reaction and [1,2]-Wittig rearrangement.

Highly chemo-, enantio-, and regioselective synthesis of α,α-disubstituted furanones by Cu-catalyzed conjugate addition.

A highly chemo-, enantio-, and regioselective synthesis of furanones bearing an α,α-disubstituted quaternary stereogenic center is reported. The Cu-catalyzed enantioselective conjugate addition of organoaluminum reagents to unsaturated ketoesters at room temperature and subsequent lactonization took place. Synthetic transformations of furanones represent facile approaches to various cyclic or acyclic compounds bearing a quaternary stereogenic center.

Creation of a Chiral All-Carbon Quaternary Center Induced by CF3 and CH3 Substituents via Cu-Catalyzed Asymmetric Conjugate Addition.

Cu-catalyzed asymmetric construction of a chiral quaternary center bearing CH3 and CF3 groups was achieved with high to excellent enantioselectivity using our originally developed ligands. The asymmetric conjugate addition of Me3Al to ß-CF3-substituted enones and unsaturated ketoesters proceeded efficiently. The use of unsaturated ketoesters gives optically active furanones in high yields with high enantioselectivities. The perfluoroalkyl-substituted enone does not seem to be favorable in the present reaction.

Stereoselective synthesis of (2Z,4E)-2,4-pentadien-1-ols via sequential 1,4-elimination reaction and [1,2]-Wittig rearrangement starting from (E)-4-alkoxy-2-butenyl benzoates.

The sequential 1,4-elimination reaction of (E)-4-alkoxy-2-butenyl benzoates and [1,2]-Wittig rearrangement gave (2Z,4E)-2,4-pentadien-1-ols stereoselectively. Z-Selective formation of intermediary vinyl ethers, whose stereochemistry was well elucidated by the "syn-effect", was achieved by treatment of the 2-butenyl benzoates with KOH in the presence of Pd catalyst. The subsequent [1,2]-Wittg rearrangement by use of n-BuLi proceeded with retention of the stereochemistry of the intermediary vinyl ethers.

Effect of multinuclear copper/aluminum complexes in highly asymmetric conjugate addition of trimethylaluminum to acyclic enones.

Al and friends: asymmetric conjugate addition of Me(3)Al to ß,ß-disubstituted α,ß-unsaturated ketones in the presence copper and L1 leads to a highly efficient construction of an all-carbon-substituted chiral quaternary center. This result is the first example of an asymmetric conjugate addition of Me(3)Al to acyclic enones to give a chiral quaternary carbon center with excellent yield and enantioselectivity under mild reaction conditions.

Cross coupling between sp3-carbon and sp3-carbon using a diborylmethane derivative at room temperature.

A novel example of the Suzuki-Miyaura cross-coupling reaction between sp(3)-carbon and sp(3)-carbon is described. The reaction of a diborylmethane derivative with allyl halides or benzyl halides proceeded efficiently in the presence of appropriate Pd-catalysts at room temperature. The present approaches provide functionalized homoallylboronates and alkylboronates with excellent regio- and chemoselectivities.

One-pot synthesis of symmetrical and unsymmetrical diarylmethanes via diborylmethane.

A one-pot synthesis of diarylmethanes from air-stable diborylmethane via the Suzuki-Miyaura cross-coupling reaction is described. The present approach realizes the synthesis of various symmetrical and unsymmetrical diarylmethanes in good to excellent yields.

Ru-catalyzed ß-selective and enantioselective addition of amines to styrenes initiated by direct arene-exchange.

A catalytic ß-selective addition of amines to styrenes proceeded in the presence of cationic Ru complexes combined with diphosphine ligands. In the reaction of α-methylstyrene, an enantioselective addition was achieved by using xylylBINAP.

Chemoselective and regiospecific Suzuki coupling on a multisubstituted sp(3)-carbon in 1,1-diborylalkanes at room temperature.

The palladium-catalyzed Suzuki-Miyaura cross-coupling on a multisubstituted sp(3)-carbon in 1,1-diborylalkanes was achieved at room temperature. The generation of a monoborate intermediate by virtue of the adjacent B atom could result in the chemoselective coupling reaction under ambient conditions.

Stereoselective synthesis of tetrasubstituted alkenylboronates via 1,1-organodiboronates.

The stereoselective synthesis of tetrasubstituted alkenylboronates was established via the lithiation/nucleophilic addition reaction of 1,1-organodiboronates to carbonyl compounds. The present approach enables the facile and practical synthesis of tetrasubstituted olefins, which are useful synthetic intermediates for further functionalizations.

The first asymmetric Sonogashira coupling for the enantioselective generation of planar chirality in paracyclophanes.

The double Sonogashira coupling of diiodoparacyclophanes with alkynes proceeded to give planarly chiral dialkynylparacyclophanes; a chiral Pd catalyst, which was prepared in situ from PdCl(2)(CH(3)CN)(2) and Taniaphos, realized the first asymmetric Sonogashira coupling with up to ca. 80% ee.

Construction of a chiral quaternary carbon center by indium-catalyzed asymmetric alpha-alkenylation of beta-ketoesters.

Construction of a nonracemic all-carbon quaternary stereocenter at the alpha-position of beta-ketoesters was achieved by way of an indium(III)-catalyzed diastereoselective alpha-alkenylation reaction of chiral enamines with 1-alkynes. The enamine bearing a chiral auxiliary derived from l-isoleucine was added to the alkyne to give an alpha-alkenylated product in excellent yield and with a stereoselectivity better than 90% ee. One can ascribe the high selectivity to a chelate intermediate involving the auxiliary and the metal atom and the high yield to efficient interactions between the indium(III) atom and the alkyne. The selectivity increased as the reaction temperature was raised to 120 degrees C and decreased at higher temperatures.

Enantioselective syntheses of various chiral multicyclic compounds with quaternary carbon stereocenters by catalytic intramolecular cycloaddition.

The intramolecular cycloaddition of 1,n-diene-ynes (n = 4-6), where alkyne and alkene moieties are connected by a 1,1-disubstituted alkene, was examined using a chiral rhodium catalyst, and various types of cycloadducts with quaternary carbon stereocenter(s) were obtained in high to excellent enantiomeric excess. In the case of 1,4-diene-ynes, tricyclic, bicyclic, and spirocyclic compounds were obtained depending upon the substituents at the 2-position of the 1,4-diene moiety and those at their alkyne termini. On the other hand, 1,5- and 1,6-diene-ynes gave tricyclic and bicyclic compounds, which included medium-sized ring systems. The mechanistic considerations for different reaction pathways and the synthetic transformation of tricyclic products into functionalized spirocyclic compounds are also described. The reaction of enediynes, where two alkyne moieties are connected by a 1,1-disubstituted alkene, was also examined, and sterically strained tricyclic compounds with two carbon stereocenters were obtained.

Efficient formation of ring structures utilizing multisite activation by indium catalysis.

Lewis acidic indium(III) salts, in particular In(NTf(2))(3), effect the conversion of alpha-(omega'-alkynyl)-beta-ketoesters and omega-alkynyl-beta-ketoesters to the corresponding cyclic products in a manner known as the Conia-ene reaction. This reaction can lead to the creation of five- to fifteen-membered-ring carbocycles and heterocycles in good to excellent yields. The synthetic features of the reaction are a relatively low catalyst loading, as low as 0.01 mol % in the best case, as well as no requirement of solvent for five-membered-ring formation and the requirement of only moderately dilute reaction conditions for medium-sized-ring formation. The high reactivity of indium salts is due to the double activation of the beta-ketoester substrate containing an acetylene function. The indium metal activates the beta-ketoester moiety by the formation of an indium enolate, and this indium metal electrophilically activates the alkyne moiety. Such a strong push-pull activation of the substrate by a single metal circumvents the disadvantage of entropic and enthalpic factors generally associated with the formation of medium- and large-sized rings. The reaction allows the ready formation of a fifteen-membered-ring carbocycle, from which dl-muscone has been synthesized.