Asymmetric total synthesis and revision of absolute configurations of azaphilone derivative felinone A

The first total synthesis of the azaphilone derivative, felinone A, was accomplished. The absolute configuration of natural felinone A was revised to be 3S, 6S, and 7R.     

Effect of shock interactions on the attitude stability of a toroidal ballute for reentry vehicles

The effect of shock interactions on the attitude stability of a reentry vehicle system with a toroidal ballute was investigated. The hypersonic wind tunnel experimental results showed that when the shock interaction occurred near or outside the ballute, an unstable oscillation of the ballute was observed. This was caused by the local high-pressure region on the ballute surface created by the shock interaction between the shock from the reentry capsule and the shock from the ballute. To avoid this unstable oscillation, the radius of the ballute should be designed to be large enough so that the shock from the capsule will be located inside the ballute, which can avoid the local high-pressure region on the ballute surface.     

Enzymatic Formation of Indolactam Scaffold by C−N Bond-Forming Cytochrome P450 Oxidases in Teleocidin Biosynthesis

Teleocidins are potent protein kinase C activators, and possess a unique indole-fused nine-membered lactam structure. Teleocidin biosynthesis starts from the formation of a dipeptide by non-ribosomal peptide synthetase (NRPS), followed by oxidative C−N bond formation by a cytochrome P450 oxidase, reverse-prenylation by a prenyltransferase, and methylation-initiated terpene cyclization by a C-methyltransferase. This minireview focuses on recent research progress toward the elucidation of the molecular basis for the remarkable P450-catalyzed intramolecular C−N bond-forming reaction, which is challenging in synthetic chemistry, to generate the indolactam scaffold. In addition, precursor-directed biosynthesis with the promiscuous P450 enzymes led to the formation of a series of unnatural and novel molecular scaffolds, including a sulfur-substituted indolactam with a different conformation from that of indolactam V.     

Effect of preparation procedure on redox states of iron in soda-lime silicate glass

The redox state of iron in soda-lime silicate glass was determined by analysis of the optical absorption bands due to Fe²⁺ and Fe³⁺ states. When raw materials containing Fe₂O₃ were heated gradually to 1400 °C, the total-Fe content of the glass was 9.4% Fe²⁺, but rapid heating at 1400 °C increased the Fe²⁺ content to 11.7%. The oxygen activity (aO₂) in the corresponding melts was measured using zirconia and Pt electrodes. The value increased with increasing temperature in the gradually heated sample and reached log(aO₂) = 0.03 at 1400 °C, but was about 2.5 times lower in the rapidly heated sample at log(aO₂) = ?0.37. After SnO addition to the raw material, oxygen activity depended strongly on heating speed: log(aO₂) at 1400 °C fell as low as ?1.8 with rapid temperature increase but was about ?0.2 or higher with gradual heating. The Fe²⁺ content of the cooled glass was consistent with the oxygen activity of the melts. The effect of heating speed was attributed to the formation of a melt layer on the surface of the raw material.     

Enantioselective Total Synthesis of (−)‐Candelalides A,B and C: Potential Kv1.3 Blocking Immunosuppressive Agents

Potential immunosuppressive agents : Candelalides A, B and C (see figure), novel blockers of the voltage‐gated potassium channel Kv1.3, have been efficiently synthesized for the first time in a convergent and unified manner starting from (+)‐5‐methyl‐Wieland–Miescher ketone. The method explored has potential for preparing various types of candelalide analogues for the structure–activity relationship studies.

     

5‐(1,2,3‐Triazol‐1‐yl)tetrazole Derivatives of an Azidotetrazole via Click Chemistry

N? C bonded (non‐bridged) 5‐(1,2,3‐triazol‐1‐yl)tetrazoles were synthesized by the Cu^I‐catalyzed 1,3‐dipolar azide–alkyne cycloaddition click reaction using 5‐azido‐N‐(propan‐2‐ylidene)‐1H‐tetrazole ( 1 ). For example, the click reaction of 1 in the presence of CuSO₄?5 H₂O and Na ascorbate at 65–70 °C for 48 h in CH₃CN/H₂O co‐solvent was found to be limited to only terminal alkynes that have electron‐withdrawing groups, CF₃C?CH ( 2 a ) and SF₅C?CH ( 2 b ), giving rise to isopropylidene‐[5‐(4‐trifluoromethyl‐1,2,3‐triazol‐1‐yl)tetrazol‐1‐yl]amine ( 3 a ) and isopropylidene‐[5‐(4‐pentafluorosulfanyl‐1,2,3‐triazol‐1‐yl)tetrazol‐1‐yl]amine ( 3 b ) in 47 % and 66 % yields, respectively. When carried out under conditions using CuI and 2,6‐lutidine as catalysts at 0 °C for 13 h in CHCl₃, the click reaction was versatile toward alkynes even those having electron‐donating groups. Properties of new products were determined and compared with those of 1 . Heats of formation, detonation pressures, detonation velocities and impact sensitivities are reported for these new 5‐(1,2,3‐triazol‐1‐yl)tetrazoles.     

The Turaev genus of an adequate knot

The Turaev genus of a knot is an obstruction to the knot being alternating. An adequate knot is a generalization of an alternating knot. A natural problem is a characterization of the Turaev genus of an adequate knot. In this paper, we show that the Turaev genus of an adequate knot is realized by the genus of the Turaev surface associated to an adequate diagram of the knot using the Khovanov homology. As a result, we obtain the additivity of the Turaev genus of adequate knots, and show that the Turaev genus of an adequate knot is “often” preserved under mutation. We also show that an n-semi-alternating knot is of Turaev genus n. This is the first examples of adequate knots of Turaev genus two or more.     

A Remark on the Courant-Friedrichs-Lewy Condition in Finite Difference Approach to PDE's

The Courant-Friedrichs-Lewy condition (The CFL condition) is appeared in the analysis of the finite difference method applied to linear hyperbolic partial differential equations. We give a remark on the CFL condition from a view point of stability, and we give some numerical experiments which show instability of numerical solutions even under the CFL condition. We give a mathematical model for rounding errors in order to explain the instability.