Castasterone,a new phytosterol with plant-hormone potency,from chestnut insect gall

A sterol which has strong potency to inclinate rice lamina was isolated from the insect gall of the chestnut tree. The structure was determined to be (22R, 23R, 24S)-2α, 3α, 22, 23-tetrahydroxy-24-methyl-5α-cholestan-6-one ($\text{1}$).     

Practical method of improving the turnability of terrain vehicles

To improve the trafficability and the turnability of the terrain vehicles, it was already pointed out in a previous report that the control of the ground contact area of the running gear such as tracks and wheels could be highly recommended. The contact area of the running gear must be as large as possible to obtain more traction, however, less contact area would be better to obtain easier turning and steering. In this paper the principle of improving the turnability for the terrain vehicle was theoretically discussed. One of the examples of the practical application of the theory developed here was proposed and applied to the terrain vehicle equipped with eight powered wheels, which was constructed as a test vehicle for this study.     

Histidine‐Containing Peptide Catalysts Developed by a Facile Library Screening Method

Although peptide catalysts have a high potential for the use as organocatalysts, the optimization of peptide sequences is laborious and time‐consuming. To address this issue, a facile screening method for finding efficient aminocatalysts from a peptide library has been developed. In the screening for the Michael addition of a malonate to an enal, a dye‐labeled product is immobilized on resin‐bound peptides through reductive amination to visualize active catalysts. This procedure allows for the monitoring of the reactivity of entire peptides without modifying the resin beads beforehand. Peptides containing histidine at an appropriate position were identified by this method. A novel function of the histidyl residue, which enhances the binding of a substrate to the catalyst by capturing an iminium intermediate, was indicated.     

Gold‐Catalyzed Cascade Cyclization of 2‐Alkynyl‐N‐Propargylanilines by Rearrangement of a Propargyl Group

Gold catalysis enables direct construction of tetracyclic fused indolines through the migration of a propargyl substituent from an aniline nitrogen atom to the C3‐position of an indole from 2‐alkynyl‐N‐propargylanilines. This reaction provides rapid access to fused three‐dimensional indolines in a single operation with the formation of four bonds and three rings.     

Model studies of 6,7-indolequinone cofactors of quinoprotein amine dehydrogenases

The electronic effects of the C-4 substituent on the physicochemical properties and reactivity of the 6,7-inodolequinone cofactors (CTQ and TTQ) have extensively been investigated with use of a series of C-4 substituted 6,7-inodolequinone derivatives (1-4). The one-electron reduction potentials of the 6,7-inodolequinone derivatives decrease with increasing the electron donating ability of the C-4 substituent (with the following order of E degrees': 4>1>2>3). The reaction of indolequinones 1-3 with benzylamine proceeds stepwise through the iminoquinone and the product-imine intermediates to give aminophenol as the final product as the case of TTQ model compound 4. The rate constants of each step have been determined by the detailed kinetic analysis, and the kinetic deuterium isotope effects have also been examined to confirm the rate-determining step. The reactivity of CTQ model compound 1 toward the amines is by one order of magnitude lower than that of TTQ model compound 4. The reactivity of indolequinones 2 and 3 is further decreased due to their stronger electron-donating substituents at C-4. A more important difference between CTQ model compound 1 and TTQ model compound 4 is the reactivity of the iminoquinone intermediate: the reaction of the CTQ model compound with amines stops at the iminoquinone formation stage at room temperature, whereas the reaction of the TTQ model compound with amines proceeds up to the aminophenol formation. Thus, the energy barrier for the rearrangement of the iminoquinone to the product-imine is higher in the CTQ model system than in the TTQ model system.     

Systematic solution-phase parallel synthesis of active vitamin D3 analogs with elongated side chains and their cell differentiation activities

Side-chain elongation of active vitamin D3 is acknowledged as a structural modification to enhance its cell differentiation activity; however, the comprehensive structure-activity relationship (SAR) as a result of this modification has not been reported. To clarify the SAR, we synthesized six analogs systematically elongated at the 24-position, 26,27-position, or both by methylene (normal A-ring series 1a-f) in a facile parallel solution-phase synthesis. Using parallel synthesis, we expanded the side chain-elongation study into two 19-exomethylene analog series: 19-nor-A-ring (4a-f) and 2-methylene-19-nor-A-ring (5a-f). In the 19-nor-A-ring analog series, the SAR induced by side-chain elongation was similar to the normal A-ring analog series, but in the 2-methylene-19-nor-A-ring series, the SAR was unique.     

Synthesis of unnatural flavonoids and stilbenes by exploiting the plant biosynthetic pathway in Escherichia coli

Flavonoids and stilbenes have attracted much attention as potential targets for nutraceuticals, cosmetics, and pharmaceuticals. We have developed a system for producing "unnatural" flavonoids and stilbenes in Escherichia coli. The artificial biosynthetic pathway included three steps. These included a substrate synthesis step for CoA esters synthesis from carboxylic acids by 4-coumarate:CoA ligase, a polyketide synthesis step for conversion of the CoA esters into flavanones by chalcone synthase and chalcone isomerase, and into stilbenes by stilbene synthase, and a modification step for modification of the flavanones by flavone synthase, flavanone 3beta-hydroxylase and flavonol synthase. Incubation of the recombinant E. coli with exogenously supplied carboxylic acids led to production of 87 polyketides, including 36 unnatural flavonoids and stilbenes. This system is promising for construction of a larger library by employing other polyketide synthases and modification enzymes.