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81.
Total Synthesis of the 7,10‐Epimer of the Proposed Structure of Amphidinolide N,Part II: Synthesis of C17–C29 Subunit and Completion of the Synthesis
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Dr. Koji Ochiai Dr. Sankar Kuppusamy Yusuke Yasui Kenji Harada Dr. Nishant R. Gupta Dr. Yohei Takahashi Prof. Dr. Takaaki Kubota Prof. Dr. Jun'ichi Kobayashi Prof. Dr. Yujiro Hayashi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(10):3287-3291
The total synthesis of 7,10‐epimer of the proposed structure of amphidinolide N was accomplished. The requisite chiral C17–C29 subunit was assembled stereoselectively via Keck allylation, Shi epoxidation, diastereoselective 1,3‐reduction, and a later oxidative synthesis of the THF framework. The C1–C13 and C17–C29 subunits were successfully coupled using a Enders RAMP “linchpin” as the C14–C16 three carbon unit, thereby controlling the chirality at C14 and C16. The labile allyl epoxy moiety was successfully constructed by Grieco–Nishizawa olefination at a final stage of the synthesis. 相似文献
82.
Copolymers of pentafluorophenylhexafluoroisopropyl methacrylate (FPPMA) with trifluoroethyl methacrylate (TFEMA) were prepared in THF solution and in bulk using azobisisobutyronitrile as a free radical initiator. The monomer reactivity ratios of TFEMA (M1) and FPPMA (M2) were calculated as r1 = 0.55 and r2 = 0.07. The refractive indices of poly(TFEMA) and poly(FPPMA) are very similar as 1.435 and 1.430, respectively, at 532 nm, and the copolymer films were transparent. The glass transition temperatures (Tg) of the copolymers were in the range of 80–90°C and showed a negative deviation from the Gordon–Taylor equation. The thermal decomposition temperature (Td) was increased with the content of FPPMA in copolymers. Low water absorption for 1:1 FPPMA/TFEMA copolymer was detected. Copolymers of FPPMA with hexafluoroisopropyl methacrylate (HFPMA) were also prepared. The monomer reactivity ratios of HFPMA (M1) and FPPMA (M2) were calculated as r1 = 0.43 and r2 = 0.10. The Tgs of the copolymers were in the range of 88–95°C and showed also a negative deviation from the Gordon–Taylor equation. Tg and Td of the copolymers were increased with the content of FPPMA. The refractive index of poly(HFPMA) (1.384 at 532 nm) is much lower than that of FPPMA homopolymer, but copolymer films obtained were clear and transparent. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
83.
Eiichi Kimura Naomi Katsube Tohru Koike Motoo Shiro Shin Aoki 《Supramolecular chemistry》2013,25(2-3):95-102
We have previously shown that the nucleobase thymine binding to Zn2+ -cyclen (cyclen=1,4,7,10-tetraazacyclododecane) complex became stronger by appending acridine, naphthalene, or quinoline rings to the cyclen. Amongst these, the pendant bis((1-naphthyl)methyl) or bis((4-quinolyl)methyl) groups yielded the most effective thymine-recognizing Zn2+ -cyclen complexes [J. Am. Chem. Soc., 121 (1999) 5426]. The present study was undertaken to find causes of the bis(aromatic) ring effect by X-ray crystal structure analysis and NMR studies. The crystal structure of the Zn2+ -bis((1-naphthyl)methyl)-cyclen complex with a deprotonated 1-methylthymine (1-MeT) failed to show the anticipated evidence for the double ~ - ~ stacking interactions between the two naphthalenes and the Zn 2+ -bound 1-MeT m (1-MeT m =N(3')-deprotonated 1-MeT). Crystal data: formula C36 H47 N7 O7 Zn, M r =755.19, monoclinic, space group P21/ c (No. 14), a =15.438(2) Å, b =14.093(3) Å, c =16.726(2) Å, g =90.53(1) V =3638.7(8) Å 3 Z =4, R =0.035, R w =0.049. However, the 1H NMR studies of Zn2= -bis((4-quinolyl)methyl)-cyclen with 1-MeT in varying H2O/CH3 CN solution showed increasing upfield shifts of Me(5') and H(6') of the Zn2+ -bound 1-MeT in more aqueous media, indicating that the double intercalation with the two quinolines became more significant in more protic environments. We conclude that the double ~ - ~ stacking effect accounts for the enhanced recognition of thymine base by the appended bis((1-naphthyl)methyl) or bis((4-quinolinyl)methyl) groups. 相似文献
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87.
Silacyclophanes possessing two disilanyl pillars were synthesized from tricyclic heteroarenes in one‐pot synthetic procedures. The step‐like anti structures of three congeners bearing two heteroarene units were revealed in single crystals by X‐ray crystallographic analysis. Depending on the structures of aromatic units, torsion angles at the disilanyl pillars altered to maintain the overall step‐like molecular structures. The structure, however, fluctuated between anti and syn conformers in a solution phase despite the presence of eight methyl groups on the ring periphery. The analysis of the coalescence temperature with NMR spectroscopy showed the fundamental energetics of the dynamics. The subtle structural differences affected the dynamic behavior of the silacyclophanes. 相似文献
88.
Yusuke Fukahori Yohei Takayama Takuya Imaoka Dr. Osamu Iwamoto Prof. Dr. Kazuo Nagasawa 《化学:亚洲杂志》2013,8(1):244-250
We present a diastereoselective synthesis of disubstituted cyclopentane 8 having a nitrogen‐containing quaternary carbon center, which is found in axinellamine A ( 5 ) and related compounds. During this work, we found that the 1,3‐dipolar cycloaddition product 24 immediately underwent intramolecular redox reaction at the newly formed morpholin‐2‐one moiety, thus affording disubstituted cyclopentane containing a tertiary amine ( 9 ) stereoselectively in good yield. The amine 9 was successfully converted into guanidine 31 , which corresponds to 8 , through iminium cation–enamine isomerization. 相似文献
89.
Wetting phenomena play important roles in several technological applications and in many physical and biological thin‐film phenomena, such as wetting, adhesion and friction. One of key issues of these studies is to control the surface energy (or wettability) dynamically for liquid transportation. We have developed a liquid crystal (LC) surface for use as a transport substrate since we expected that the surface energy of an LC surface can be controlled rapidly using an electric field. The rapid control of the polarisability (or wettability) of a liquid crystalline surface by an electric field has been demonstrated, together with the transportation of a liquid microdroplet. 相似文献
90.
Nobutaka Yamaoka Kohei Sumida Itsuki Itani Hiroko Kubo Yusuke Ohnishi Sho Sekiguchi Dr. Toshifumi Dohi Prof. Dr. Yasuyuki Kita 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(44):15004-15011
Metal‐free oxidative C? C coupling by using polyalkoxybenzene‐derived diaryliodonium(III) salts as both the oxidant and aryl source has been developed. These salts can induce single‐electron‐transfer (SET) oxidation to yield electron‐rich arenes and subsequently transfer the polyalkoxyphenyl group into in situ generated aromatic radical cations to produce biaryl products. The reaction is promoted by a Lewis acid that activates the iodonium salts. It has been revealed that the reactivity of the salts under acidic conditions is quite different to their known behavior under basic conditions. The reactivity preference of a series of iodonium salts in the SET oxidation and their ligand transfer abilities have been systematically investigated and the results are summarized in this report. 相似文献