Synthesis of 3,4‐Fused Tricyclic Indoles Using 3‐Alkylidene Indolines as Versatile Precursors

In this personal account, our recent studies of novel synthetic methods of 3,4‐fused tricyclic indole derivatives using 3‐alkylidene indoline derivatives as versatile precursors are discussed. Two types of cascade reactions producing 3,4‐fused tricyclic 3‐alkylidene indolines were developed based on a palladium‐catalyzed intramolecular Heck insertion to an allene‐allylic amination cascade and a platinum‐catalyzed intramolecular Friedel‐Crafts type C?H coupling‐allylic amination cascade. Furthermore, three types of 3,4‐fused tricyclic indoles were accessible from a single 3‐alkylidene indoline precursor via acid‐promoted olefin isomerization or oxidative treatments. The application of the developed methods to the synthesis of natural products bearing a 3,4‐fused tricyclic indole skeleton, (?)‐aurantioclavine, fargesine, and synthetic studies of dragmacidin E are also highlighted.     

Search for solar axions with mass around 1 eV using coherent conversion of axions into photons

A search for solar axions has been performed using an axion helioscope which is equipped with a 2.3-m long 4 T superconducting magnet, a gas container to hold dispersion-matching gas, PIN-photodiode X-ray detectors, and a telescope mount mechanism to track the sun. A mass region around ma=1 eV$m_a=1\text{eV}$ was newly explored. From the absence of any evidence, analysis sets a limit on axion–photon coupling constant to be g_aγγ<5.6–13.4×¹⁰⁻¹⁰ GeV⁻¹$g_{a\gamma \gamma }<5.6\text{–}13.4\times {10}^{\mathrm{-10}}{\text{GeV}}^{\mathrm{-1}}$ for the axion mass of 0.84<ma<1.00 eV$0.84<m_a<1.00\text{eV}$ at 95% confidence level. It is the first result to search for the axion in the g_aγγ–ma$g_{a\gamma \gamma }\text{–}{m}_a$ parameter region of the preferred axion models with a magnetic helioscope.     

Investigation of Mizoroki‐Heck coupling polymerization as a catalyst‐transfer condensation polymerization for synthesis of poly(p‐phenylenevinylene)

Mizoroki‐Heck coupling polymerization of 1,4‐bis[(2‐ethylhexyl)oxy]‐2‐iodo‐5‐vinylbenzene ( 1 ) and its bromo counterpart 2 with a Pd initiator for the synthesis of poly(phenylenevinylene) (PPV) was investigated to see whether the polymerization proceeds in a chain‐growth polymerization manner. The polymerization of 1 with ^tBu₃PPd(Tolyl)Br ( 10 ) proceeded even at room temperature when 5.5 equiv of Cy₂NMe (Cy = cyclohexyl) was used as a base, but the molecular weight distribution of PPV was broad. The polymerization of 2 hardly proceeded at room temperature under the same conditions. In the polymerization of 1 , PPV with H at one end and I at the other was formed until the middle stage, and the polymer end groups were converted into tolyl and H in the final stage. The number‐average molecular weight (M_n) did not increase until about 90% monomer conversion and then sharply increased after that, indicating conventional step‐growth polymerization. The occurrence of step‐growth polymerization, not catalyst‐transfer chain‐growth polymerization, may be interpreted in terms of low coordination ability of H‐Pd(II)‐X(^tBu₃P) (X = Br or I), formed in the catalytic cycle of the Mizoroki‐Heck coupling reaction, to π‐electrons of the PPV backbone; reductive elimination of H‐X from this Pd species with base would take place after diffusion into the reaction mixture. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 543–551     

Control of chain ends of polyesters in polycondensation of AA and BB monomers by use of solid‐phase reagent

For selective synthesis of linear polyester having a functional group at one end, polycondensation between 1,4‐butanediol ( 1a ) and sebacoyl chloride ( 2a ) and between 1,12‐dodecanediol ( 1b ) and isophthaloyl chloride ( 2b ) was conducted in the presence of oxime resin or oxime silica gel, followed by cleavage of the formed polyester from the solid‐phase support with aniline. Matrix‐assisted laser desorption ionization time‐of‐flight mass spectra and ¹H NMR spectra of the cleaved polyester showed that the products contained not only polyester with anilide at one end ( poly 1 ), but also polyester with anilides at both ends ( poly 2 ). The product ratio of poly 1 to poly 2 ( poly 1 / poly 2 ) was dependent on monomers, monomer concentration, feed ratio of monomer to oxime moiety in the support, oxime content in the support, reaction solvent, and the nature of the support. Polyester with a high poly 1 / poly 2 ratio of 81/21 and moderate molecular weight (M_n = 1430 g/mol) was obtained by polycondensation of 1b and 2b in the presence of oxime silica gel in dichloromethane. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1379–1386     

Constraints in the variational principle for stationary states

Constraints in the variational principle for stationary states (VPSS) are classified in accordance with Dirac’s constrained classical mechanics and the time-dependent variational principle (TDVP). All of the VPSS constraints are required to belong to the first-class TDVP as constants of motion to ensure the real-valuedness of the Lagrange multipliers. The VPSS constraints are further classified as either first-class or second-class. The first-class VPSS constraints are constants of variation with symmetry-adapted wave functions. If the representation basis for the constraint operators is incomplete, however, the first-class VPSS constraints lead to broken-symmetry solutions. The nondegenerate energies of \({}^2E'\) at the \(D_{3h}\) geometry in the Jahn–Teller distortion of H\(_3\) are presented as an example of a problem with broken-symmetry. An ad hoc adjustment is suggested by considering the second-class pseudo-VPSS constraints with new adiabatic parameters.     

Second-harmonic generation with a high-index-clad waveguide

Theoretical and experimental analyses of second-harmonic generation (SHG) with a high-index-clad waveguide are reported. It was found that confinement of the propagation modes and the overlap between the fields of fundamental and second-harmonic waves could be increased in this waveguide. This structure was achieved in an x-cut MgO:LiNbO (3) quasi-phase-matched (QPM) waveguide by use of Nb(2)O(5) as a cladding layer. With the QPM SHG device, harmonic blue light of 5.5 mW at the 434-nm wavelength was generated with a normalized conversion efficiency of 1200%/W cm(2).     

Concise synthesis of indole-fused 1,4-diazepines through copper(I)-catalyzed domino three-component coupling-cyclization-N-arylation under microwave irradiation

Indole-fused benzo-1,4-diazepines were synthesized by copper-catalyzed domino three-component coupling-indole formation- N-arylation under microwave irradiation from a simple N-mesyl-2-ethynylaniline. This method was also applicable to the formation of heterocycle-fused 1,4-diazepines.     

Stepwise elongation effect on the two-photon absorption of self-assembled butadiyne porphyrins

Butadiyne-porphyrin dimer arrays, which were generated by complementary coordination of the central zinc atom to imidazolyl followed by metathesis, were elongated stepwise and their 2PA properties were explored.