We report a solid‐phase strategy for total synthesis of the peptidic natural product yaku'amide B ( 1 ), which exhibits antiproliferative activity against various cancer cells. Its linear tridecapeptide sequence bears four β,β‐dialkylated α,β‐dehydroamino acid residues and is capped with an N‐terminal acyl group (NTA) and a C‐terminal amine (CTA). To realize the Fmoc‐based solid‐phase synthesis of this complex structure, we developed new methods for enamide formation, enamide deprotection, and C‐terminal modification. First, traceless Staudinger ligation enabled enamide formation between sterically encumbered alkenyl azides and newly designed phosphinophenol esters. Second, application of Eu(OTf)3 led to chemoselective removal of the enamide Boc groups without detaching the resin linker. Finally, resin‐cleavage and C‐terminus modification were simultaneously achieved with an ester–amide exchange reaction using CTA and AlMe3 to deliver 1 in 9.1 % overall yield (24 steps from the resin). 相似文献
A Ni(OAc)2‐catalyzed C?H coupling of 8‐aminoquinoline‐derived benzamides with epoxides has been developed. The reaction proceeds with concomitant removal of the 8‐aminoquinoline auxiliary to form the corresponding 3,4‐dihydroisocoumarins directly. Additionally, the nickel catalysis is stereospecific, and the cis‐ and trans‐epoxides are converted into the corresponding cis‐ and trans‐dihydroisocoumarins with retention of configuration, which is complementary to previously reported palladium catalysis. Moreover, while still preliminary, the C ?H functionalization is also achieved in the presence of modified NiCl2 catalysts. 相似文献
Atomic capture probabilities of negative pions in some metal hydrides were measured. The capture by a hydrogen atom was detected by means of a pair of the annihilation rays of 0 which had been produced by the charge-exchange reaction of – with the capturing hydrogen nucleus (proton). This method ensures a high sensitivity and reliability of the measurements. The probabilities obtained were in agreement with previous measurements except for palladium hydride, which showed a much smaller probability than that given in the literature. The atomic capture of – is well described in the framework of the large mesic molecular model, in which the proportionality constant reflects the chemical states of the capturing atoms and also the neighboring ones. 相似文献
The transfer of negative pions captured by hydrogen to heavier atoms has been investigated in a series of alcohols by measuring both 2 rays from 0 decay and pionic X rays. Capture rates for the pionic hydrogen of different chemical states in the molecule were determined from a comparison between the data for the ordinary compound and the deuterated one. The external transfer in the condensed phase was revealed by the dependence of the capture rate of hydrogen on the number of carbon atoms in the alkyl group. The influence of the chemical structure on the transfer process is discussed with respect to the large difference between the relative transfer rates,
C=1.5±0.2 and
O = 4.5±0.4, corresponding to carbon and oxygen, respectively. 相似文献
The fundamental motivation to study the non-mesonic weak decay (NMWD) of Λ hypernuclei is that it provides the unique channel for the information of the baryon–baryon weak interaction in SU3f group. The relative strength of the two main channels of NMWD whose decay processes are the Λp → np and Λn → nn has been the long standing puzzle during last several decades. The puzzling status has been settled down recently with the Γn / Γp value converging to ${\sim 0.5}$ . The large experimental values of Γn / Γp of the previous measurements turned out to be due to the surprisingly large contribution of the competing three-body NMWD, ΛNN → nNN process. This paper discusses about the first measurement of the branching ratio of the three-body NMWD process and the renormalized intra-nuclear cascade method adopted to disentangle the contribution of the three-body process out of those due to final state interaction. And the prospects of the more accurate measurement of the three-body process also are presented. 相似文献
Porous surface patterns are used in a wide variety of practical applications. Honeycomb‐patterned porous polymer films are good templates for preparing porous surfaces due to their simple fabrication and the arrangement of pores on the surface. Catechol groups include in adhesive protein of mussels have attracted much attention due to their highly and substrate‐independent adhesive properties. In this paper, highly and substrate‐independent adhesive honeycomb‐patterned porous polymer films are prepared by using amphiphilic copolymer having catechol moieties. Furthermore, porous surface patterns are transferred on various organic or inorganic substrates by wet etching with using adhesive honeycomb films as templates.
Anisotropic morphologies and the phase behaviour of a hydrogen-bonded LC polymer obtained by photopolymerization in two kinds of LC solvent are discussed. The hydrogen-bonded LC monomer, 4-(6-acryloyloxyhexyloxy) benzoic acid (A6OBA), was photopolymerized in 4-cyano-4'-hexyloxybiphenyl (6OCB) and in 4-cyano-4'-undecyloxybiphenyl (11OCB), which show a nematic phase and a smectic A phase, respectively. After photo-polymerization, the LC media were removed by extraction and the pure polymer was observed by scanning electron microscopy. SEM images showed that the polymer possessed fibrous morphology with a fibre diameter of a few micrometers, based on polymerization-induced phase separation. The overall geometries reflected typical LC characteristics such as schlieren and focal-conic fan textures. It was found that the hydrogen bond between benzoic acid groups in the monomer was rigid enough to fix the anisotropic phase-separated structure forming during the early stage of phase separation; however, it could not permanently maintain the fibre structure due to dissociation at elevated temperature. X-ray measurements revealed that a well developed layer structure of the hydrogen-bonded mesogen existed in the polymer obtained from the smectic phase of 11OCB, whereas a polymer layer structure could develop only partially from the nematic phase of 6OCB. 相似文献
In the presence of CaCl2, dimethylsilyl (DMS) enolates smoothly reacted with aldehydes under mild conditions to give aldol adducts in good to high yields. The catalytic activities of various metal and tetrabutylammonium salts have revealed that CaCl2 works as a Lewis base catalyst to activate DMS enolates. The CaCl2-promoted reaction proceeded even in the presence of water or in pure water. This catalytic system was applicable to the aldol reaction with aqueous aldehydes such as formalin. 相似文献