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91.
Tetsuo Ogawa 《Phase Transitions》2013,86(1-2):93-128
Photoinduced structural phase transitions via excited electronic states are discussed theoretically using a one-dimensional model composed of localized electrons and lattices under the adiabatic or diabatic approximation. We show that the global structural change by photoexcitation only at a site is possible, and we clarify conditions for the occurrence of such phenomena. Spatiotemporal dynamics of nonequilibrium first-order phase transitions is also investigated in detail in terms of photoinduced nucleations and domino processes of the domain boundaries (domain walls), which are in striking contrast to the mean-field dynamics. In the adiabatic regime, after the spontaneous emission of a photon, an initial local structural change (i) remains locally, (ii) induces cooperatively a global structural change, or (iii) disappears and returns to the initial phase. Dynamical features of the case (ii) are characterized by the deterministic (semichaotic) domino process; domain walls between the two phases move determinis-tically at a constant velocity (with changing speed) without further spontaneous emissions in the case of strong (weak) dissipation. In the diabatic regime, similar three types of structural change exist. The domain-wall dynamics is described as the stochastic domino process, which is accompanied by the successive radiative transitions. A new theoretical treatment is also proposed to study crossover between the adiabatic and diabatic regimes. 相似文献
92.
An efficient and practical isatin-based oxidative domino protocol has been developed for the facile synthesis of 2-aminobenzamides and 2-aminobenzoates. The robust nature of this reaction system is reflected by accessible starting materials, room temperature and high-yield gram-scale synthesis. 相似文献
93.
Palladium‐Catalyzed Domino CH/NH Functionalization: An Efficient Approach to Nitrogen‐Bridged Heteroacenes
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Natsuyo Kamimoto Dr. Dieter Schollmeyer Dr. Koichi Mitsudo Prof.Dr. Seiji Suga Prof.Dr. Siegfried R. Waldvogel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(22):8257-8261
Palladium‐catalyzed domino C?H/N?H functionalization for the synthesis of novel nitrogen‐bridged thienoacenes and 10H‐benzo[4,5]thieno[3,2‐b]indole derivatives from dihaloarene is reported. This domino sequence consists of initial C?H functionalization of the benzo[b]thiophene moiety, followed by Buchwald–Hartwig coupling. This transformation is also useful for the synthesis of highly π‐extended compounds. 相似文献
94.
Gang Yan Bereket L. Zekarias Dr. Xiaoyu Li Victor A. Jaffett Ilia A. Guzei Prof. Dr. Jennifer E. Golden 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(11):2486-2492
A highly efficient 2-chloroquinazolin-4(3H)-one rearrangement was developed that predictably generates either twisted-cyclic or ring-fused guanidines in a single operation, depending on the presence of a primary versus secondary amine in the accompanying diamine reagent. Exclusive formation of twisted-cyclic guanidines results from pairing 2-chloroquinazolinones with secondary diamines. Use of primary amine-containing diamines permits a domino quinazolinone rearrangement/intramolecular cyclization, gated through (E)-twisted-cyclic guanidines, to afford ring-fused N-acylguanidines. This scalable, structurally tolerant transformation generated 55 guanidines and delivered twisted-cyclic guanidines with robust plasma stability and an abbreviated total synthesis of an antitumor ring-fused guanidine (4 steps, 55 % yield). 相似文献
95.
Yong Zhang Min Yang Chengli Jia Prof. Min Ji 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(60):13709-13713
A method for the synthesis of novel fused four-ring quinoxaline skeleton has been described by an I2 promoted sp3 C−H functionalization between 1,2,3,3-tetramethyl-3H-indolium iodides and 1,2-diamines. This transformation proceeds smoothly under metal- and peroxide-free conditions through a sequential iodination, oxidation, annulation and rearrangement. Moreover, 8,9-dichloro-5,12,12-trimethyl-2-(trifluoromethyl)-5,12-dihydroquinolino[2,3-b]quinoxaline showed good photophysical properties and was used in live cell imaging, indicating the potential value of this skeleton as a fluorophore in probes. 相似文献
96.
Minghui He Shun Jiang Ruixin Xu Jianwen Yang Zhaohua Zeng Guangxue Chen 《Journal of polymer science. Part A, Polymer chemistry》2014,52(11):1560-1569
A detailed evaluation of the kinetics of domino free radical photopolymerization (DFRP) based on phototriggered base proliferation reaction and redox initiation was described in the condition of eliminating the heat of polymerization via reacting in the thin polymer films. First, domino photoinitiating system made a substantial breakthrough in the photoefficiency of amine generation in contrast to photocaged base system, exhibiting marked improvement in the photosensitivity. Second, both the structural feature of base amplifier (BA) and reaction temperature as two important factors impacting the proliferation rate have been detailed. Third, different domino photoinitiating components, such as BAs, peroxides, and acrylates, were investigated in the thin polymer films. It is shown that both primary and secondary BAs are efficient catalysts for DFRP. Furthermore, polymerization rate shows a consistent dependence on the pKa value of the proliferated amine. Finally, remarkable post conversion after irradiation was achieved in DFRP. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1560–1569 相似文献
97.
Tomáš Čarný Dr. Ronan Rocaboy Dr. Antonin Clemenceau Prof. Dr. Olivier Baudoin 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(43):19142-19146
The 1,4-palladium shift strategy allows the functionalization of remote C−H bonds that are difficult to reach directly. Reported here is a domino reaction proceeding by C(sp3)−H activation, 1,4-palladium shift, and amino- or alkoxycarbonylation, which generates a variety of amides and esters bearing a quaternary β-carbon atom. Mechanistic studies showed that the aminocarbonylation of the σ-alkylpalladium intermediate arising from the palladium shift is fast using PPh3 as the ligand, and leads to the amide rather than the previously reported indanone product. 相似文献
98.
Doris Chen Elizabeth V. Jones Corey W. Williams Tan-Khang N. Huynh Tristan C. McPhail Prof. Dr. Stefan France 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(52):e202201368
Herein, a SnCl4-catalyzed intramolecular, interrupted homo-Nazarov cascade biscyclization to access angular (hetero)aryl-fused polycycles is reported. Subsequent decarboxylation of the readily enolizable products afforded the angular products in up to 71 % yield over two steps, with the trans-diastereomers as the major products. The cyclopropyl homo-Nazarov cyclization precursors were formed using a scalable and modular synthetic route that, ultimately, offers access to 6,6,6-, 6,6,5-, 6,5,6-, 6,6,5,6-, and 6,6,6,5-fused angular polycyclic products. To showcase the rigor and utility of the method, an 8-step total synthesis of (±)-1-oxoferruginol, an antibacterial aromatic abietane diterpenoid, was disclosed. 相似文献
99.
Dual Palladium(II)/Tertiary Amine Catalysis for Asymmetric Regioselective Rearrangements of Allylic Carbamates
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Dr. Johannes Moritz Bauer Dr. Wolfgang Frey Prof. Dr. René Peters 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(16):5767-5777
The streamlined catalytic access to enantiopure allylic amines as valuable precursors towards chiral β‐ and γ‐aminoalcohols as well as α‐ and β‐aminoacids is desirable for industrial purposes. In this article an enantioselective method is described that transforms achiral allylic alcohols and N‐tosylisocyanate in a single step into highly enantioenriched N‐tosyl protected allylic amines via an allylic carbamate intermediate. The latter is likely to undergo a cyclisation‐induced [3,3]‐rearrangement catalysed by a planar chiral pentaphenylferrocene palladacycle in cooperation with a tertiary amine base. The otherwise often indispensable activation of palladacycle catalysts by a silver salt is not required in the present case and there is also no need for an inert gas atmosphere. To further improve the synthetic value, the rearrangement was used to form dimethylaminosulfonyl‐protected allylic amines, which can be deprotected under non‐reductive conditions. 相似文献
100.
Domino Staudinger/aza‐Wittig/Mannich Reaction: An Approach to Diversity of Di‐ and Tetrahydropyrrole Scaffolds
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Dr. Anna S. Pavlova Dr. Olga A. Ivanova Dr. Alexey O. Chagarovskiy Nikolay S. Stebunov Dr. Nikolay V. Orlov Dr. Alexey N. Shumsky Dr. Ekaterina M. Budynina Dr. Victor B. Rybakov Prof. Dr. Igor V. Trushkov 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(50):17967-17971
A highly efficient and selective domino reaction producing valuable di‐ and tetrahydropyrrole‐based skeletons from azidoethyl‐substituted CH‐acids and (thio)carbonyl compounds has been developed. By involving the additional functional groups in starting compounds into the domino reaction or postmodification of the primary reaction products, the simple construction of the pharmaceutically relevant three‐ and polycyclic azaheterocyclic scaffolds was demonstrated. 相似文献