Asymmetric synthesis of α,α-disubstituted α-amino alcohol derivatives

Herein we report the asymmetric synthesis of α,α-disubstituted α-amino alcohol derivatives 22, 25 and 26, key intermediates of a novel immunomodulator, using Seebach’s method. This synthetic method can be applied to the large scale synthesis of chiral sphingosine 1-phosphate-1 (S1P₁) receptor agonists, with significant improvements to the previously reported method with regard to the reaction temperature.     

Vicinal C-functionalization of alkenes. Pd/light-induced multicomponent coupling reactions leading to functionalized esters and lactones

Under photoirradiation conditions using a xenon light, and in the presence of PdCl(2)(PPh(3))(2) as a catalyst, four-component coupling reactions comprising of α-substituted iodoalkanes, alkenes, carbon monoxide, and alcohols proceeded smoothly to give functionalized esters in good yields. When alkenyl alcohols were used as acceptor alkenes, three-component coupling reactions accompanied by intramolecular esterification proceeded to give lactones in good yields. The present reaction system represents the vicinal C-functionalization of alkenes.     

On Complementary Spaces of the Lizorkin Spaces

Let S(Rⁿ){\cal S}(R^n) be the Schwartz space on R ⁿ . For a subspace V ì S(Rⁿ)V\subset {\cal S}(R^n), if a subspace W ì S(Rⁿ)W \subset {\cal S}(R^n) satisfies the condition that S(Rⁿ){\cal S}(R^n) is a direct sum of V and W, then W is called a complementary space of V in S(Rⁿ){\cal S}(R^n). In this article we give complementary spaces of two kinds of the Lizorkin spaces in S(Rⁿ){\cal S}(R^n).     

Metabolism of tetrahydrobiopterin: Its relevance in monoaminergic neurons and neurological disorders

(6R)‐L‐erythro‐5,6,7,8‐tetrahydrobiopterin (BH4) is an essential cofactor for aromatic amino acid hydroxylases, such as phenylalanine hydroxylase (PAH), tyrosine hydroxylase (TH), tryptophan hydroxylase, and nitric oxide synthase, which catalyze physiologically important reactions in mammals. The biosynthesis and metabolism of BH4 is usually studied mostly in the liver and only slightly in the brain, as the BH4 level in the liver is relatively high because BH4 is required for the reaction of PAH. We found that GTP (guanosine triphosphate) cyclohydrolase I, an enzyme for the biosynthesis of BH4, is a causative gene for DOPA (3,4‐dihydroxyphenylalanine)‐responsive dystonia (also called Segawa's disease), and that partial deficiency of BH4 leads to the dysfunction of the nigrostriatal dopaminergic neurons without hyperphenylalaninemia. We analyzed BH4‐deficient mice that were produced by disruption of a BH4‐synthesizing gene by a gene‐knockout technique. We found that the protein amount of TH was highly dependent on the amount of BH4, especially in nerve terminals. Our research suggests that BH4 metabolism in the brain should be different from that in the liver, and that altered metabolism of BH4 should lead to neuropsychiatric disorders including Parkinson's disease. © 2008 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 8: 378–385; 2008: Published online in Wiley InterScience ( www.interscience.wiley.com ) DOI 10.1002/tcr.20166     

Semiconductor-catalyzed photooxygenation of aromatic olefins

Irradiation of semiconductors (TiO₂ and CdS) suspended in organic solvents containing 1,1-diphenylethylene and its derivatives under oxygen afforded the corresponding epoxides and benzophenone. A possible mechanism is discussed.     

Current-voltage characteristics of charge-ordered organic crystals

The current-voltage characteristics of layered organic crystals theta-(BEDT-TTF)2MZn(SCN)4 (M = Cs, Rb) follow the power law with a large exponent (e.g., 8.4 at 0.29 K for M = Cs) over a wide range of currents in the low-temperature insulating state. The power-law characteristics are attributed to electric field-induced unbinding of electron-hole pairs that are thermally excited in the background of the two-dimensional charge order. The magnitude of crossover electric fields from Ohmic to the power-law characteristics indicates that the electron-electron Coulomb interaction is significantly long-ranged: The screening length is greater than 10 molecule sites.     

10 GHz, 2.4 ps pulse generation using a single-stage dual-drive Mach-Zehnder modulator

This Letter reports on picosecond pulse generation at a repetition of 10 GHz by using a single-stage electro-optic LiNbO(3) Mach-Zehnder modulator, stressing the simplicity of its setup. It is analytically and experimentally proved that dual-arm modulation with in-phase sinusoidal signals having slightly different amplitudes generated a highly coherent optical comb with a great spectral flatness and a parabolic phase relationship in its spectrum. The generated comb was Fourier synthesized and shaped into an ultrashort pulse train with an optical bandpass filter and a dispersive fiber. The pulse source was highly stable, exhibiting an ultralow timing jitter of less than 130 fs.     

Asymmetric total syntheses of two phlegmarine-type alkaloids, lycoposerramines-V and -W, newly isolated from Lycopodium serratum

Two new Phlegmarine-type alkaloids, lycoposerramines-V and -W, were isolated from Lycopodium serratum, and their structures including the absolute configuration were established by asymmetric total synthesis involving such key steps as Johnson-Claisen rearrangement, asymmetric allylation, and ring-closing metathesis (RCM)- or SmI(2)-mediated stereoselective piperidine ring construction.