Solid‐Phase Total Synthesis of Yaku'amide B Enabled by Traceless Staudinger Ligation

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).     

Nickel‐Catalyzed Stereospecific C−H Coupling of Benzamides with Epoxides

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.     

Measurement of atomic capture probabilities of negative pions in metal hydrides

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.     

Measurements of transfer process in pion capture by a series of alcohols

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.     

Three-Body ΛNN → nNN Nonmesonic Weak Decay Process of Λ Hypernuclei

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 SU3 _f 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 Γ _n / Γ _p value converging to ${\sim 0.5}$ . The large experimental values of Γ _n / Γ _p 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.     

Fabrication of Mussel‐Inspired Highly Adhesive Honeycomb Films Containing Catechol Groups and Their Applications for Substrate‐Independent Porous Templates

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.

     

Synthesis and thermoresponsive property of end‐functionalized poly(N‐isopropylacrylamide) with pyrenyl group

N–Isopropylacrylamide (NIPAM) was polymerized using 1‐pyrenyl 2‐chloropropionate (PyCP) as the initiator and CuCl/tris[2‐(dimethylamino)ethyl]amine (Me₆TREN) as the catalyst system. The polymerizations were performed using the feed ratio of [NIPAM]₀/[PyCP]₀/[CuCl]₀/[Me₆TREN]₀ = 50/1/1/1 in DMF/water of 13/2 at 20 °C to afford an end‐functionalized poly(N‐isopropylacrylamide) with the pyrenyl group (Py–PNIPAM). The characterization of the Py–PNIPAM using matrix‐assisted laser desorption ionization time‐of‐flight mass spectrometry provided the number–average molecular weight (M_n,MS). The lower critical solution temperature (LCST) for the liquid–solid phase transition was 21.7, 24.8, 26.5, and 29.3 °C for the Py–PNIPAMs with the M_n,MS's of 3000, 3400, 4200, and 5000, respectively; hence, the LCST was dramatically lowered with the decreasing M_n,MS. The aqueous Py–PNIPAM solution below the LCST was characterized using a static laser light scattering (SLS) measurement to determine its molar mass, M_w,SLS. The aqueous solutions of the Py–PNIPAMs with the M_n,MS's of 3000, 3400, 4200, and 5000 showed the M_w,SLS of 586,000, 386,000, 223,000, and 170,000, respectively. Thus, lowering the LCST for Py–PNIPAM should be attributable to the formation of the PNIPAM aggregates. The LCST of 21.7 °C for Py–PNIPAM with the M_n,MS of 3000 was effectively raised by adding β‐cyclodextrin (β‐CD) and reached the constant value of ～26 °C above the molar ratio of [β‐CD]/[Py–PNIPAM] = 2/1, suggesting that β‐CD formed an inclusion complex with pyrene in the chain‐end to disturb the formation of PNIPAM aggregates, thus raising the LCST. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1117–1124, 2006     

Morphological studies of a hydrogen-bonded LC polymer obtained by photopolymerization in LC solvents

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.     

Lewis base-promoted aldol reaction of dimethylsilyl enolates in aqueous dimethylformamide: use of calcium chloride as a Lewis base catalyst.

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.