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1.
Shunsuke Shimo Dr. Kohei Takahashi Prof. Nobuharu Iwasawa 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(15):3790-3794
A new chiral probe molecule for mono-alcohols is developed by using 1,2-dihydro-1-hydroxy-2,3,1-benzodiazaborine (DAB) bearing an acridine moiety 1 . In the presence of mono-alcohols, DAB 1 forms borate 2 by boronic ester formation, followed by coordination of the acridine moiety to the boron atom. Borate 2 has a chiral center on the boron atom and works as a stereodynamic circular dichroism (CD) probe molecule for chiral mono-alcohols based on the π–π interaction between the acridine moiety and the carbon–carbon unsaturated moiety on mono-alcohols. 相似文献
2.
3.
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 下载免费PDF全文
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
4.
Simultaneous Induction of Axial and Planar Chirality in Arene–Chromium Complexes by Molybdenum‐Catalyzed Enantioselective Ring‐Closing Metathesis 下载免费PDF全文
Prof.Dr. Ken Kamikawa Dr. Sachie Arae Dr. Wei‐Yi Wu Chihiro Nakamura Prof.Dr. Tamotsu Takahashi Prof.Dr. Masamichi Ogasawara 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(13):4954-4957
The molybdenum‐catalyzed asymmetric ring‐closing metathesis of the various Cs‐symmetric (π‐arene)chromium substrates provides the corresponding bridged planar‐chiral (π‐arene)chromium complexes in excellent yields with up to >99 % ee. With a bulky and unsymmetrical substituent, such as N‐indolyl or 1‐naphthyl, at the 2‐positions of the η6‐1,3‐diisopropenylbenzene ligands, both biaryl‐based axial chirality and π‐arene‐based planar chirality are simultaneously induced in the products. The axial chirality is retained even after the removal of the dicarbonylchromium fragment, and the chiral biaryl/heterobiaryl compounds are obtained with complete retention of the enantiopurity. 相似文献
5.
Daisuke Uraguchi Fumito Ueoka Naoya Tanaka Tomohito Kizu Wakana Takahashi Takashi Ooi 《Angewandte Chemie (International ed. in English)》2020,59(28):11456-11461
Catalysis by chiral weakly‐coordinating anions (WCAs) remains underdeveloped due to the lack of a molecular design strategy for exploiting their characteristics, such as the non‐nucleophilic nature. Here, we report the development of a chiral borate ion comprising an O,N,N,O‐tetradentate backbone, which ensures hitherto unattainable structural robustness. Upon pairing with a proton, the hydrogen borate acts as an effective catalyst for the asymmetric Prins‐type cyclization of vinyl ethers, providing access to structurally and stereochemically defined dihydropyrans. The key to selectivity control is the distinct ability of the borate ion to discriminate the prochiral faces of the acyclic oxonium ion intermediate and dictate the regiochemical outcome. We anticipate that this study paves the way for exploring the untapped potential of WCA catalysis for selective chemical synthesis. 相似文献
6.
Prof. Isao Fujii Dr. Makoto Hashimoto Kaori Konishi Akiko Unezawa Haruka Sakuraba Kenta Suzuki Harue Tsushima Miho Iwasaki Satsuki Yoshida Akane Kudo Rina Fujita Aika Hichiwa Koharu Saito Dr. Takashi Asano Dr. Jun Ishikawa Dr. Daigo Wakana Dr. Yukihiro Goda Ayumi Watanabe Mamoru Watanabe Yui Masumoto Dr. Junichiro Kanazawa Dr. Hajime Sato Prof. Masanobu Uchiyama 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(22):8542-8548
Shimalactones A and B are neuritogenic polyketides possessing characteristic oxabicyclo[2.2.1]heptane and bicyclo[4.2.0]octadiene ring systems that are produced by the marine fungus Emericella variecolor GF10. We identified a candidate biosynthetic gene cluster and conducted heterologous expression analysis. Expression of ShmA polyketide synthase in Aspergillus oryzae resulted in the production of preshimalactone. Aspergillus oryzae and Saccharomyces cerevisiae transformants expressing ShmA and ShmB produced shimalactones A and B, thus suggesting that the double bicyclo-ring formation reactions proceed non-enzymatically from preshimalactone epoxide. DFT calculations strongly support the idea that oxabicyclo-ring formation and 8π-6π electrocyclization proceed spontaneously after opening of the preshimalactone epoxide ring through protonation. We confirmed the formation of preshimalactone epoxide in vitro, followed by its non-enzymatic conversion to shimalactones in the dark. 相似文献
7.
Kazuki Inaba Masato Endo Naoto Iibuchi Prof. Dr. Daisuke Takahashi Prof. Dr. Kazunobu Toshima 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(45):10222-10225
The first total synthesis of terpioside B ( 1 ) has been accomplished. Key steps include the stereoselective installments of a set of challenging 1,2-cis-glycosidic linkages. Thus, α(1,4)-linked d -galactoside was effectively constructed from a 1,2-anhydrogalactose donor and an unprotected 1,6-anhydrogalactose acceptor by using a boron-mediated aglycon delivery (BMAD) method. In addition, α-l -fucofuranosides were stereoselectively and simultaneously constructed by remote group-assisted 1,2-cis-α-stereoselective glycosylations. 相似文献
8.
Dr. Toshiro Takao Dr. Yuta Takahashi Masataka Kai 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(29):e202200327
A dicationic triruthenium complex containing a μ3-η3-C3 ring, [(Cp*Ru)3(μ3-η3-C3MeH2−)(μ3-CH)(μ-H)]2+ ( 1 a , Cp*=η5-C5Me5), reacted with ammonia to yield a μ-amido complex, [(Cp*Ru)3(μ3-η3-CHCMeCH) (μ3-CH)(μ-NH2)]2+ ( 5 ), via N−H bond scission. Subsequent treatment with base resulted in C−N bond formation to yield a μ3-η2:η2-1-azabutadien-4-yl complex, [(Cp*Ru)3(μ3-CH)(μ3-η2:η2-NH=CH−CMe=CH−)]+ ( 6 a ). The azaruthenacyclopentadiene skeleton was alternatively synthesized by the photolysis of mono-cationic complex [(Cp*Ru)3(μ3-η3-C3RH2−)(μ3-CH)]+ ( 2 a ; R=Me, 2 b ; R=H) in the presence of ammonia. The C3 ring skeleton was broken via the electron transfer to the π*(C−C) orbital in the C3 ring, and a transiently generated unsaturated μ3-allylic species can take up ammonia, resulting in N−H bond scission followed by C−N bond formation. 相似文献
9.
Takahiro Moriyama Daiki Mizukami Dr. Makoto Yoritate Dr. Kazuteru Usui Dr. Daisuke Takahashi Dr. Eisuke Ota Prof. Dr. Mikiko Sodeoka Prof. Dr. Tadashi Ueda Prof. Dr. Satoru Karasawa Prof. Dr. Go Hirai 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(11):e202103925
Minimalist photo-reactive probes, which consist of a photo-reactive group and a tag for detection of target proteins, are useful tools in chemical biology. Although several diazirine-based and aryl azide-based minimalist probes are available, no keto-based minimalist probe has yet been reported. Here we describe minimalist probes based on a 2-thienyl-substituted α-ketoamide bearing an alkyne group on the thiophene ring. The 3-alkyne probe showed the highest photo-affinity labeling efficiency. 相似文献
10.
Computational studies have often been carried out on hydrogen-terminated nanographenes (NGs). These structures are, however, far from those deduced from experimental observations, which have suggested armchair edges with two carboxy groups on the edges as dominant. We conducted computational studies on NGs consisting of C42, C60, C78, C96, C142, and C174 carbon atoms with hydrogen, carboxy, and N-methyl imide-terminated armchair edges. DFT calculations inform distorted basal planes and similar HOMO-LUMO gaps, indicating that the edge oxidation and functionalization do not very influence the electronic structure. Comparison of observed UV-vis spectra of carboxy- and N-octadecyl chain terminated NGs with calculated spectra of model NGs informs the contribution of π-π* transitions on the basal plane to the absorptions in the visible region. A dimeric structure of NG and octadecyl-installed NG demonstrate that both the distorted basal planes and the steric contacts among the functional groups widen the surface-to-surface distance thereby allowing the invasion of solvent molecules between the surfaces. This picture is consistent with the improved solubility of edge-modified NGs. 相似文献