Successive Synthesis of Regular and Asymmetric Star-Branched Polymers by Iterative Methodology Based on Living Anionic Polymerization Using Functionalized 1,1-Diphenylethylene Derivatives

In order to achieve the successive synthesis of star-branched polymers, we have developed a new iterative methodology which involves only three sets of the reactions in each iterative process: (a) a coupling reaction of a living anionic polymer with 1,1-bis(3-chloromethylphenyl)ethylene to prepare a DPE-chain-functionalized polymer, (b) an addition reaction of sec-BuLi to the DPE-chain-functionalized polymer, followed by treatment with 1-(4-(4-bromobutyl)phenyl)-1-phenylethylene to prepare a new DPE-chain-functionalized polymer whose DPE is separated by four methylene units from the main chain, and (c) a coupling reaction of 1,1-bis(3-chloromethylphenyl)ethylene with the polymer anion derived from the newly prepared DPE-chain-functionalized polymer and sec-BuLi. With this methodology, a series of well-defined 4-arm, 8-arm, and 16-arm regular star-branched polystyrenes as well as 4-arm A₂B₂, 8-arm A₄B₄, and 16-arm A₈B₈ asymmetric star-branched polymers comprising polystyrene and poly(α-methylstyrene) segments have been successively synthesized.     

In situ generation of 3,3,3-trifluoropropanal and its use for carbon-carbon bond-forming reactions

The DIBAL reduction of 2-phenylethyl 3,3,3-trifluoro-2-methylpropionate 2 at -78 degrees C afforded the aluminum acetal 3, and this intermediate, on worming up to 0 degrees C, was found to slowly decompose into the corresponding aldehyde 4, which smoothly reacted with appropriate nucleophiles in a one-pot manner in good to excellent yields with up to 93% diastereoselectivity.     

Sequential reaction intermediates in aliphatic C-H bond functionalization initiated by a bis(mu-oxo)dinickel(III) complex

The reaction of [Ni2(OH)2(Me2-tpa)2]2+ (1) (Me2-tpa = bis(6-methyl-2-pyridylmethyl)(2-pyridylmethyl)amine) with H2O2 causes oxidation of a methylene group on the Me2-tpa ligand to give an N-dealkylated ligand and oxidation of a methyl group to afford a ligand-based carboxylate and an alkoxide as the final oxidation products. A series of sequential reaction intermediates produced in the oxidation pathways, a bis(mu-oxo)dinickel(III) ([Ni2(O)2(Me2-tpa)2]2+ (2)), a bis(mu-superoxo)dinickel(II) ([Ni2(O2)2(Me2-tpa)2]2+ (3)), a (mu-hydroxo)(mu-alkylperoxo)dinickel(II) ([Ni2(OH)(Me2-tpa)(Me-tpa-CH2OO)]2+ (4)), and a bis(mu-alkylperoxo)dinickel(II) ([Ni2(Me-tpa-CH2OO)2]2+ (5)), was isolated and characterized by various physicochemical measurements including X-ray crystallography, and their oxidation pathways were investigated. Reaction of 1 with H2O2 in methanol at -40 degrees C generates 2, which is extremely reactive with H2O2, producing 3. Complex 2 was isolated only from disproportionation of the superoxo ligands in 3 in the absence of H2O2 at -40 degrees C. Thermal decomposition of 2 under N2 generated an N-dealkylated ligand Me-dpa ((6-methyl-2-pyridylmethyl)(2-pyridylmethyl)amine) and a ligand-coupling dimer (Me-tpa-CH2)2. The formation of (Me-tpa-CH2)2 suggests that a ligand-based radical Me-tpa-CH2* is generated as a reaction intermediate, probably produced by H-atom abstraction by the oxo group. An isotope-labeling experiment revealed that intramolecular coupling occurs for the formation of the coupling dimer. The results indicate that the rebound of oxygen to Me-tpa-CH2* is slower than that observed for various high-valence bis(mu-oxo)dimetal complexes. In contrast, the decomposition of 2 and 3 in the presence of O2 gave carboxylate and alkoxide ligands, respectively (Me-tpa-COO- and Me-tpa-CH2O-), instead of (Me-tpa-CH2)2, indicating that the reaction of Me-tpa-CH2* with O2 is faster than the coupling of Me-tpa-CH2* to generate ligand-based peroxyl radical Me-tpa-CH2OO*. Although there is a possibility that the Me-tpa-CH2OO* species could undergo various reactions, one of the possible reactive intermediates, 4, was isolated from the decomposition of 3 under O2 at -20 degrees C. The alkylperoxo ligands in 4 and 5 can be converted to a ligand-based aldehyde by either homolysis or heterolysis of the O-O bond, and disproportionation of the aldehyde gives a carboxylate and an alkoxide via the Cannizzaro reaction.     

First total synthesis of artepillin C established by o,o'-diprenylation of p-halophenols in water

We have demonstrated that prenylation of p-halophenols was dependent on the solvent effect and succeeded in o,o'-diprenylation of p-halophenols in water. Following the Mizoroki-Heck coupling of the diprenyl-p-iodophenol 3c with methyl acrylate and then hydrolysis, we first synthesized artepillin C [3-(4-hydroxy-3,5-di(3-methyl-2-butenyl)phenyl)-2(E)-propenoic acid] (1), which is a biologically active constituent of propolis. These reactions may be applicable to the synthesis of various useful natural products such as 2,4,6-trisubstituted phenol derivatives.     

Formal Synthesis of Sarain A: Intramolecular Cycloaddition of an Eight‐Membered Cyclic Nitrone to Construct the 2‐Azabicyclo[3.3.1]nonane Framework

An enantioselective route to the tetracyclic skeleton of sarain A has been developed. Asymmetric reduction of an ynone introduced a chiral center which was transferred to the contiguous tertiary stereogenic centers through an Ireland–Claisen rearrangement. The 2‐azabicyclo[3.3.1]nonane framework was constructed by an unprecedented intramolecular cycloaddition of an eight‐membered cyclic nitrone. Using the steric bias of the bicyclic system, the quaternary carbon atom was constructed by a stereoselective aldol reaction. Further ring formations were performed by ring‐closing metathesis for the 13‐membered ring and an iodoamidation reaction for the pyrrolidine ring. The present synthesis has successfully provided an alternative route to the late‐stage intermediate of Overman’s synthesis.     

Synthesis and characterization of benzo[1,2-b:3,4-b':5,6-b']trithiophene (BTT) oligomers

Two dimers (2 and 3), dendritic tetramer (4), hexamer (5), and decamer (6) of benzo[1,2-b:3,4-b':5,6-b']trithiophene (BTT), a potential π-core unit with C(3h) symmetry, were synthesized, characterized, and evaluated for possible use as organic semiconductors. Single crystal X-ray analyses of the dimers (2 and 3) revealed that they have planar molecular structures with dihedral angles of almost 180° between two BTT units. In accordance with the rigid and planar molecular structure, the unsubstituted dimer (2) is poorly soluble, whereas the octyl-substituted dimer (3) has improved solubility. Although the solubility of the dendritic tetramer (4) is decreased, further extended systems, i.e., the dendritic hexamer (5) and decamer (6), have solubilities better than that of 4. With increasing numbers of BTT units in the molecule, the experimentally determined energy levels of HOMO shift upward slightly and the HOMO-LUMO energy gaps become smaller, but the extent of HOMO destabilization and reduction of the HOMO-LUMO gap are not significant. Taking into account the energy levels of the frontier orbitals, 3-6 could be useful as p-channel organic semiconductors rather than n-channel. In fact, the spin-coated thin film of 3 with edge-on molecular orientation acted as an active channel of field-effect transistors that showed hole mobilities as high as 0.14 cm(2) V(-1) s(-1), indicating that the BTT core is a useful π-conjugated system for application to organic semiconductors, although 4-6 gave FET characteristics rather inferior to those of 3, owing to their amorphous nature in the thin film state.     

Palladium-catalyzed denitrogenation reaction of 1,2,3-benzotriazin-4(3H)-ones incorporating isocyanides

1,2,3-Benzotriazin-4(3H)-ones and 1,2,3,4-benzothiatriazine 1,1(2H)-dioxide reacted with isocyanides in the presence of a palladium catalyst to give 3-(imino)isoindolin-1-ones and 3-(imino)thiaisoindoline 1,1-dioxides, respectively, in high yield. An intermediate azapalladacycle was generated through denitrogenation of the triazine moiety, and an isocyanide was incorporated therein.     

The roles of molecular structure and effective optical symmetry in evolving dipolar chromophoric building blocks to potent octopolar nonlinear optical chromophores

A series of mono-, bis-, tris-, and tetrakis(porphinato)zinc(II) (PZn)-elaborated ruthenium(II) bis(terpyridine) (Ru) complexes have been synthesized in which an ethyne unit connects the macrocycle meso carbon atom to terpyridyl (tpy) 4-, 4'-, and 4'-positions. These supermolecular chromophores, based on the ruthenium(II) [5-(4'-ethynyl-(2,2';6',2'-terpyridinyl))-10,20-bis(2',6'-bis(3,3-dimethyl-1-butyloxy)phenyl)porphinato]zinc(II)-(2,2';6',2'-terpyridine)(2+) bis-hexafluorophosphate (RuPZn) archetype, evince strong mixing of the PZn-based oscillator strength with ruthenium terpyridyl charge resonance bands. Potentiometric and linear absorption spectroscopic data indicate that for structures in which multiple PZn moieties are linked via ethynes to a [Ru(tpy)(2)](2+) core, little electronic coupling is manifest between PZn units, regardless of whether they are located on the same or opposite tpy ligand. Congruent with these experiments, pump-probe transient absorption studies suggest that the individual RuPZn fragments of these structures exhibit, at best, only modest excited-state electronic interactions that derive from factors other than the dipole-dipole interactions of these strong oscillators; this approximate independent character of the component RuPZn oscillators enables fabrication of nonlinear optical (NLO) multipoles with extraordinary hyperpolarizabilities. Dynamic hyperpolarizability (β(λ)) values and depolarization ratios (ρ) were determined from hyper-Rayleigh light scattering (HRS) measurements carried out at an incident irradiation wavelength (λ(inc)) of 1300 nm. The depolarization ratio data provide an experimental measure of chromophore optical symmetry; appropriate coupling of multiple charge-transfer oscillators produces structures having enormous averaged hyperpolarizabilities (β(HRS) values), while evolving the effective chromophore symmetry from purely dipolar (e.g., Ru(tpy)[4-(Zn-porphyrin)ethynyl-tpy](PF(6))(2), β(HRS) = 1280 × 10(-30) esu, ρ = 3.8; Ru(tpy)[4'-(Zn-porphyrin)ethynyl-tpy](PF(6))(2), β(HRS) = 2100 × 10(-30) esu, ρ = 3.8) to octopolar (e.g., Ru[4,4'-bis(Zn-porphyrin)ethynyl-tpy](2)(PF(6))(2), β(HRS) = 1040 × 10(-30) esu, ρ = 1.46) via structural motifs that possess intermediate values of the depolarization ratio. The chromophore design roadmap provided herein gives rise to octopolar supermolecules that feature by far the largest off-diagonal octopolar first hyperpolarizability tensor components ever reported, with the effectively octopolar Ru[4,4'-bis(Zn-porphyrin)ethynyl-tpy](2)(PF(6))(2) possessing a β(HRS) value at 1300 nm more than a factor of 3 larger than that determined for any chromophore having octopolar symmetry examined to date. Because NLO octopoles possess omnidirectional NLO responses while circumventing the electrostatic interactions that drive bulk-phase centrosymmetry for NLO dipoles at high chromophore concentrations, the advent of octopolar NLO chromophores having vastly superior β(HRS) values at technologically important wavelengths will motivate new experimental approaches to achieve acentric order in both bulk-phase and thin film structures.