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1.
Yulu Jiang Dr. Taro Ozaki Mei Harada Tadachika Miyasaka Dr. Hajime Sato Dr. Kazunori Miyamoto Dr. Junichiro Kanazawa Dr. Chengwei Liu Prof. Dr. Jun-ichi Maruyama Dr. Masaatsu Adachi Dr. Atsuo Nakazaki Prof. Dr. Toshio Nishikawa Prof. Dr. Masanobu Uchiyama Dr. Atsushi Minami Prof. Dr. Hideaki Oikawa 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(41):18152-18158
Lolitrems are tremorgenic indole diterpenes that exhibit a unique 5/6 bicyclic system of the indole moiety. Although genetic analysis has indicated that the prenyltransferase LtmE and the cytochrome P450 LtmJ are involved in the construction of this unique structure, the detailed mechanism remains to be elucidated. Herein, we report the reconstitution of the biosynthetic pathway for lolitrems employing a recently established genome-editing technique for the expression host Aspergillus oryzae. Heterologous expression and bioconversion of the various intermediates revealed that LtmJ catalyzes multistep oxidation to furnish the lolitrem core. We also isolated the key reaction intermediate with an epoxyalcohol moiety. This observation allowed us to establish the mechanism of radical-induced cyclization, which was firmly supported by density functional theory calculations and a model experiment with a synthetic analogue. 相似文献
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Dr. Nozomi Mihara Dr. Yasuyuki Yamada Dr. Hikaru Takaya Prof. Yasutaka Kitagawa Dr. Kazunobu Igawa Prof. Katsuhiko Tomooka Prof. Hiroshi Fujii Prof. Kentaro Tanaka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(13):3369-3375
Development of supramolecular methods to further activate a highly reactive intermediate is a fascinating strategy to create novel potent catalysts for activation of inert chemicals. Herein, a supramolecular approach to enhance the oxidizing ability of a high-valent oxo species of a nitrido-bridged iron porphyrinoid dimer that is a known potent molecular catalyst for light alkane oxidation is reported. For this purpose, a nitrido-bridged dinuclear iron complex of porphyrin-phthalocyanine heterodimer 3 5+, which is connected through a fourfold rotaxane, was prepared. Heterodimer 3 5+ catalyzed ethane oxidation in the presence of H2O2 at a relatively low temperature. The site-selective complexation of 3 5+ with an additional anionic porphyrin (TPPS4−) through π–π stacking and electrostatic interactions afforded a stable 1:1 complex. It was demonstrated that the supramolecular post-synthetic modification of 3 5+ enhances its catalytic activity efficiently. Moreover, supramolecular conjugates achieved higher catalytic ethane oxidation activity than nitrido-bridged iron phthalocyanine dimer, which is the most potent iron-oxo-based molecular catalyst for light-alkane oxidation reported so far. Electrochemical measurements proved that the electronic perturbation from TPPS4− to 3 5+ enhanced the catalytic activity. 相似文献
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Mitsunori Fukaya Shota Nagamine Dr. Taro Ozaki Yaping Liu Miina Ozeki Taro Matsuyama Dr. Kazunori Miyamoto Prof. Dr. Hirokazu Kawagishi Prof. Dr. Masanobu Uchiyama Prof. Dr. Hideaki Oikawa Dr. Atsushi Minami 《Angewandte Chemie (International ed. in English)》2023,62(44):e202308881
Mushroom terpenoids are biologically and chemically diverse fungal metabolites. Among them, melleolides are representative sesquiterpenoids with a characteristic protoilludane skeleton. In this study, we applied a recently established hot spot knock-in method to elucidate the biosynthetic pathway leading to 1α-hydroxymelleolide. The biosynthesis of the sesquiterpene core involves the cytochrome P450 catalyzing stepwise hydroxylation of the Δ6-protoilludene framework and a stereochemical inversion process at the C5 position catalyzed by short-chain dehydrogenase/reductase family proteins. The highlight of the biosynthesis is that the flavoprotein Mld7 catalyzes an oxidation-triggered double-bond shift accompanying dehydration and acyl-group-assisted substitution with two different nucleophiles at the C6 position to afford the Δ7-protoilludene derivatives, such as melleolide and armillarivin. The complex reaction mechanism was proposed by DFT calculations. Of particular importance is that product distribution is regulated by interaction with the cell membrane. 相似文献
8.
Miharu Eguchi Minsu Han Yusuke Asakura Jonathan P. Hill Joel Henzie Katsuhiko Ariga Alan E. Rowan Watcharop Chaikittisilp Yusuke Yamauchi 《Angewandte Chemie (International ed. in English)》2023,62(46):e202307615
Reactions occurring at surfaces and interfaces necessitate the creation of well-designed surface and interfacial structures. To achieve a combination of bulk material (i.e., framework) and void spaces, a meticulous process of “nano-architecting” of the available space is necessary. Conventional porous materials such as mesoporous silica, zeolites, and metal–organic frameworks lack advanced cooperative functionalities owing to their largely monotonous pore geometries and limited conductivities. To overcome these limitations and develop functional structures with surface-specific functions, the novel materials space-tectonics methodology has been proposed for future materials synthesis. This review summarizes recent examples of materials synthesis based on designing building blocks (i.e., tectons) and their hybridization, along with practical guidelines for implementing materials syntheses and state-of-the-art examples of practical applications. Lastly, the potential integration of materials space-tectonics with emerging technologies, such as materials informatics, is discussed. 相似文献
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Although various synthetic methodologies including organic synthesis, polymer chemistry, and materials science are the main contributors to the production of functional materials, the importance of regulation of nanoscale structures for better performance has become clear with recent science and technology developments. Therefore, a new research paradigm to produce functional material systems from nanoscale units has to be created as an advancement of nanoscale science. This task is assigned to an emerging concept, nanoarchitectonics, which aims to produce functional materials and functional structures from nanoscale unit components. This can be done through combining nanotechnology with the other research fields such as organic chemistry, supramolecular chemistry, materials science, and bio-related science. In this review article, the basic-level of nanoarchitectonics is first presented with atom/molecular-level structure formations and conversions from molecular units to functional materials. Then, two typical application-oriented nanoarchitectonics efforts in energy-oriented applications and bio-related applications are discussed. Finally, future directions of the molecular and materials nanoarchitectonics concepts for advancement of functional nanomaterials are briefly discussed. 相似文献
10.
David Pertuit Tayebe Baghery Lotfabad Anne‐Claire Mitaine‐Offer Tomofumi Miyamoto Chiaki Tanaka Marie‐Aleth Lacaille‐Dubois 《Helvetica chimica acta》2015,98(5):611-617
Two new triterpene glycosides, 1 and 2 , together with three known ones, were isolated from roots of Acanthophyllum laxiusculum Schiman ‐Czeika . The structures of the new compounds were established by extensive 1D‐ and 2D‐NMR spectroscopic experiments and MS analyses as 23‐O‐β‐D ‐galactopyranosylgypsogenic acid 28‐O‐{β‐D ‐glucopyranosyl‐(1→2)‐6‐O‐[4‐carboxy‐3‐hydroxy‐3‐methyl‐1‐oxobutyl]‐β‐D ‐glucopyranosyl‐(1→6)}‐[β‐D ‐glucopyranosyl‐(1→3)]‐β‐D ‐galactopyranosyl ester ( 1 ) and gypsogenic acid 28‐O‐{β‐D ‐glucopyranosyl‐(1→2)‐6‐O‐[4‐carboxy‐3‐hydroxy‐3‐methyl‐1‐oxobutyl]‐β‐D ‐glucopyranosyl‐(1→6)}‐[β‐D ‐glucopyranosyl‐(1→3)]‐β‐D ‐galactopyranosyl ester ( 2 ). 相似文献