Total synthesis of myceliothermophins A-E

Total synthesis of an antitumor compound myceliothermophin A and related compounds based on a convergent synthetic strategy was investigated. A common decalin skeleton of myceliothermophins was stereoselectively constructed by an IMDA reaction. The fully elaborated precursor of myceliothermophins was obtained via aldol reaction of N-protected γ-methoxylactam with decalin aldehyde. By using Teoc group for the protection of nitrogen atom of lactam ring, selective deprotection prior to the hydrolysis of methoxyaminal moiety was successfully achieved to obtain γ-methoxylactams (myceliothermophins C and D). Subsequent hydrolysis of these compounds afforded the corresponding γ-hydroxylactam, and myceliothermophins A and B in high yield. Myceliothermophin E was also synthesized by dehydration of the obtained γ-hydroxylactams. The absolute configurations of myceliothermophins A-E were also successfully determined.     

Amphiphilic liquid‐crystalline 4‐miktoarm star copolymers with a siloxane junction leading to cylindrically nanostructured templates for a siloxane‐based nanodot array

Well‐defined A₃B‐, A₂B₂‐, and AB₃‐type 4‐miktoarm star copolymers (M_n = 10,500–16,200, M_w/M_n = 1.16–1.18) consisting of poly(ethylene oxide) (PEO) and polymethacrylate bearing an azobenzene mesogen (PMA(Az)) as the arms and cyclotetrasiloxane as the core unit were synthesized using a combined route composed of a thiol‐ene click reaction and atom transfer radical polymerization. Microphase‐separated structures of the star copolymers in thin films with a thickness of approximately 100 nm were investigated by GISAXS and TEM. The A₃B‐type star‐(PEO)₃[PMA(Az)]₁ copolymer formed a more highly ordered PEO cylinder array with perpendicular alignment in the PMA(Az) matrix than that of the corresponding linear‐type block copolymer. The center‐to‐center distance of the PEO cylinders and the cylinder diameter were 13 and 4 nm, respectively. The highly ordered star‐(PEO)₃[PMA(Az)]₁ thin film was directly transferred to a siloxane‐based nanodot array by oxygen reactive ion etching. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1175–1188     

Study of optical response of spinel oxide by utilizing IR-THz spectromicroscopy

We performed a spectromicroscopic measurement on LiV₂O₄ in IR-THz (25 meV–1.5 eV) from 6–300 K under high pressures up to 20 GPa by using a DAC at the spectromicroscopy station (BL43IR) at SPring-8. At 40 K, a clear metal–insulator change was observed above 6 GPa in the optical conductivity spectra. The newly developed peak structure around 1 eV reflects the pseudo-gap forming under pressure at 40 K.     

New and efficient synthesis of azabicyclo[4.4.0]alkane amino acids by Rh-catalyzed cyclohydrocarbonylation

[reaction: see text] Highly efficient syntheses of azabicyclo[4.4.0]alkane amino acids were achieved by Rh-catalyzed cyclohydrocarbonylation of dipeptides bearing a terminal olefin moiety and a heteroatom nucleophile.