A Selective Synthesis of 3,3-Di-C-(hydroxymethyl)-3-deoxy-furanorono-1,4-lactone in the Formose Reaction

Abstract

The formose reaction, by which a complex mixture of sugars and sugar alcohols (the so-called formose) are produced by the base-catalyzed condensation of formaldehyde, has received much attention in connection with the prebiotic synthesis of carbohydrates² and the microbial utilization of formose.^3–5 Formose, however, has not been useful yet, because of the complexity of this product mixture (Fig. 1a). Therefore, it seemed desirable to make the reaction more selective.     

On the induced‐fit mechanism of substrate‐enzyme binding structures of nylon‐oligomer hydrolase

We present a detailed computational investigation of the induced‐fit motion in a nylon‐oligomer hydrolase (NylB) upon substrate binding. To this aim, we resort on the recently introduced parallel cascade selection molecular dynamics approach, allowing for an accelerated access to the set of conformational changes from an open‐ to a closed‐state structure to form the enzyme‐substrate complex in a specific induce‐fit mechanism. The structural investigation is quantitatively complemented by free energy analyses within the umbrella sampling algorithm accompanied by weighted histogram analysis. We find that the stabilization free energy is about 1.4 kcal/mol, whereas the highest free energy barrier to be overcome is about 2.3 kcal/mol. Conversely, the energetic contribution for the substrate binding is about 20 kcal/mol, as estimated from Generalized Born/Surface Area. This means that the open‐close induced‐fit motion could occur frequently once the substrate binds to the open state of NylB. © 2014 Wiley Periodicals, Inc.     

Biosynthesis of Indole Diterpene Lolitrems: Radical‐Induced Cyclization of an Epoxyalcohol Affording a Characteristic Lolitremane Skeleton

Lolitrems are tremorgenic indole diterpenes that exhibit a unique 5/6 bicyclic system of the indole moiety. Although genetic analysis has indicated that the prenyltransferase LtmE and the cytochrome P450 LtmJ are involved in the construction of this unique structure, the detailed mechanism remains to be elucidated. Herein, we report the reconstitution of the biosynthetic pathway for lolitrems employing a recently established genome‐editing technique for the expression host Aspergillus oryzae. Heterologous expression and bioconversion of the various intermediates revealed that LtmJ catalyzes multistep oxidation to furnish the lolitrem core. We also isolated the key reaction intermediate with an epoxyalcohol moiety. This observation allowed us to establish the mechanism of radical‐induced cyclization, which was firmly supported by density functional theory calculations and a model experiment with a synthetic analogue.     

Half‐Sandwich Iridium Complexes Bearing a Diprotic Glyoxime Ligand: Structural Diversity Induced by Reversible Deprotonation

Synthesis and deprotonation reactions of half‐sandwich iridium complexes bearing a vicinal dioxime ligand were studied. Treatment of [{Cp*IrCl(μ‐Cl)}₂] (Cp*=η⁵‐C₅Me₅) with dimethylglyoxime (LH₂) at an Ir:LH₂ ratio of 1:1 afforded the cationic dioxime iridium complex [Cp*IrCl(LH₂)]Cl ( 1 ). The chlorido complex 1 undergoes stepwise and reversible deprotonation with potassium carbonate to give the oxime–oximato complex [Cp*IrCl(LH)] ( 2 ) and the anionic dioximato(2?) complex K[Cp*IrCl(L)] ( 3 ) sequentially. Meanwhile, twofold deprotonation of the sulfato complex [Cp*Ir(SO₄)(LH₂)] ( 4 ) resulted in the formation of the oximato‐bridged dinuclear complex [{Cp*Ir(μ‐L)}₂] ( 5 ). X‐ray analyses disclosed their supramolecular structures with one‐dimensional infinite chain ( 1 and 2 ), hexagonal open channels ( 3 ), and a tetrameric rhomboid ( 4 ) featuring multiple intermolecular hydrogen bonds and electrostatic interactions.     

Organic electroluminescent device with aromatic amine-containing polymer as a hole transport layer (II): Poly(arylene ether sulfone)-containing tetraphenylbenzidine

Organic electroluminescent devices were fabricated using a poly(arylene ether sulfone)-containing tetraphenylbenzidine (PTPDES) and tris(8-quinolinolato)-aluminum(III) complex, Alq, as the hole transport layer and the electron-transporting emitter layer, respectively. A device structure of glass substrate/indium—tin oxide (ITO)/PTPDES/Alq/Mg : Ag was employed. Hole injection from ITO through the PTPDES layer to the Alq layer and concomitant electroluminescence from the Alq layer were observed. Bright green light with a luminance of 14,000 cd/m² was observed at a drive voltage of 14 V, indicating that the polymer possesses a high hole mobility and a high electron-blocking capability.     

An intense terahertz radiation source at the Compact ERL

The Compact ERL is an energy recovery LINAC (ERL) test facility that is planned for KEK. The circumference of the recirculation path will be 70 m. Initially, the beam energy will be about 65 MeV and the current about 10 mA. Although the primary purpose of the machine is to aid the development of the key technologies that are essential for building an ultra-brilliant new synchrotron light source based on an ERL, the Compact ERL itself has great potential as an intense source of terahertz radiation. To generate the intense terahertz radiation, an electron bunch of a very short bunch length is required and bunch compression is inevitable. We discuss the parameters of the Compact ERL, present the results of a simulation of bunch compression, and make an estimate of the generated coherent synchrotron radiation.     

Tandem Cyclization of Alkynylmetals Bearing a Remote Leaving Group via Cycloalkylidene Carbenes

Treatment of terminal alkynes bearing a remote leaving group with MNR(2) (M = Li, Na, K) gives bicyclo[n.3.0]-1-alkenes (n = 3, 4). The tandem cyclization proceeds through a mechanism involving exo-cyclization of an alkynylmetal intermediate and intramolecular C-H insertion of the resulting carbenoid.     

A Facile Route to Indolo

Treatment of 1-(2'-bromobenzyl)-3,4-dihydroisoquinolines 2 in the presence of K(2)CO(3) in boiling DMF efficiently provided a variety of alkoxy-substituted indolo[2,1-a]isoquinolines 3. Application of this cyclization to 7-benzyloxyisoquinoline derivatives, followed by further elaboration of the resultant 2-benzyloxy-5,6-dihydroindolo[2,1-a]isoquinolines 16a,b, led to the formal synthesis of dibenzopyrrocoline alkaloids, (+/-)-cryptaustoline (1a) and (+/-)-cryptowoline (1b).