- Sequence-controlled radical polymerization of N-substituted maleimides with 1-methylenebenzocycloalkanes and the characterization of the obtained copolymers with excellent thermal resistance and transparency
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The radical copolymerization of N-methyl, ethyl, n-butyl, and 2-ethylhexylmaleimides (RMIs) with 1-methylenebenzocycloalkanes (BCms) was carried out to fabricate thermally stable and transparent polymer materials. The copolymerization reactivity of BCms significantly depended on the carbon number of the ring structure of BCms. The analyses of the comonomer-copolymer composition curves and theoretical calculations results revealed that the sequence-controlled copolymerization of RMIs with BCms occurred in alternating and 2:1 fashions according to the BCms reactivity, which depends on the coplanarity of the exomethylene moiety and the benzene ring. The alternating and high-molecular-weight copolymers of BCms and RMIs exhibited excellent thermal and optical properties. We have demonstrated that the radical copolymerization of RMIs is useful not only as the method for high-performance transparent polymer production but also as the tool for the fundamental research of radical polymerization mechanism.
- Hisano, Miki,Takeda, Kyota,Takashima, Tsutomu,Jin, Zhengzhe,Shiibashi, Akira,Matsumoto, Akikazu
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- Intermolecular [4 + 2] process of N-acyliminium ions with simple olefins for construction of functional substituted-1,3-oxazinan-2-ones
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An efficient approach to functionalized 4,6-disubstituted-and 4,6,6-trisubstituted-1,3-oxazinan-2-ones skeleton has been developed through the reaction of semicyclic N,O-acetals 4a and 4b with 1,1-disubstituted ethylenes 5 or 8. As a result of such a [4 +
- Han, Xiaoli,Nie, Xiaodi,Feng, Yiman,Wei, Bangguo,Si, Changmei,Lin, Guoqiang
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supporting information
p. 3526 - 3530
(2021/06/12)
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- Photoinduced [3+2] Annulation of Alkene with o-Iodoanilines: An Expedient Approach to Indolines
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A highly regioselective [3+2] cyclization of alkenes with 2-iodoanilines under the irradiation of UV light is described. This general, metal-free strategy facilitates the direct preparation of 2-mono-/disubstituted indolines as well as spiroindolines through alkene carboamination in one step. Mechanistic studies suggested that the photochemical protocol proceeded via a radical pathway.
- Zhao, Xinxin,Guo, Lin,Yang, Chao,Xia, Wujiong
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p. 1341 - 1348
(2020/11/19)
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- Visible-Light-Induced Meerwein Fluoroarylation of Styrenes
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An unprecedented approach for assembling a broad range of 1,2-diarylethane derivatives with fluorine-containing fully substituted carbon centers was developed. The protocol features straightforward operation, proceeds under metal-free condition, and accommodates a large variety of synthetically useful functionalities. The critical aspect to the success of this novel transformation lies in using aryldiazonium salts as both aryl radical progenitor and also as single electron acceptor which elegantly enables a radical-polar crossover manifold.
- Tang, Hai-Jun,Zhang, Bin,Xue, Fei,Feng, Chao
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p. 4040 - 4044
(2021/05/26)
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- Bridged Stilbenes: AIEgens Designed via a Simple Strategy to Control the Non-radiative Decay Pathway
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To broaden the application of aggregation-induced emission (AIE) luminogens (AIEgens), the design of novel small-molecular dyes that exhibit high fluorescence quantum yield (Φfl) in the solid state is required. Considering that the mechanism of
- Igawa, Kazunobu,Iwai, Riki,Konishi, Gen-ichi,Morokuma, Keiji,Sairi, Amir Sharidan,Sasaki, Shunsuke,Suenobu, Tomoyoshi,Suzuki, Satoshi
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supporting information
p. 10566 - 10573
(2020/04/15)
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- Aqueous ZnCl2 Complex Catalyzed Prins Reaction of Silyl Glyoxylates: Access to Functionalized Tertiary α-Silyl Alcohols
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An efficient Prins reaction of silyl glyoxylates in the presence of an aqueous ZnCl2 complex as a catalyst was developed, providing functionalized tertiary α-silyl alcohols in high yields under mild conditions. A preliminary investigation indicated that the aqueous ZnCl2 complex acted as a dual functional catalyst of Br?nsted and Lewis acid to activate the carbonyl groups of silyl glyoxylates via a dual-activation model.
- Han, Man-Yi,Pan, Hong,Li, Pinhua,Wang, Lei
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p. 5825 - 5837
(2020/05/22)
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- Electrochemically Enabled Carbohydroxylation of Alkenes with H2O and Organotrifluoroborates
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Unprecedented hydroxy-alkynylation and -alkenylation reactions of arylalkenes have been developed through electrochemically enabled addition of an organotrifluoroborate reagent and H2O across the double bond of the alkene. The use of electrochemistry to promote these oxidative alkene 1,2-difunctionalization reactions not only obviates the need for transition-metal catalysts and oxidizing reagents but also ensures high regio- and chemoselectivity to afford homopropargylic or homoallylic alcohols. The possibility of extending the electrochemical alkene difunctionalization strategy to other alkene carbo-heterofunctionalization reactions has been demonstrated.
- Xiong, Peng,Long, Hao,Song, Jinshuai,Wang, Yaohui,Li, Jian-Feng,Xu, Hai-Chao
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supporting information
p. 16387 - 16391
(2018/11/23)
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- Direct β-Selective Hydrocarboxylation of Styrenes with CO2 Enabled by Continuous Flow Photoredox Catalysis
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The direct β-selective hydrocarboxylation of styrenes under atmospheric pressure of CO2 has been developed using photoredox catalysis in continuous flow. The scope of this methodology was demonstrated with a range of functionalized terminal styrenes, as well as α-substituted and β-substituted styrenes.
- Seo, Hyowon,Liu, Aofei,Jamison, Timothy F.
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supporting information
p. 13969 - 13972
(2017/10/17)
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- B(C6F5)3-Catalyzed Ring Opening and Isomerization of Unactivated Cyclopropanes
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Catalytic amounts of B(C6F5)3 promote the ring opening and subsequent isomerization of a series of unactivated cyclopropanes to afford terminal olefins in good yields when a hydrosilane and 2,6-dibromopyridine are employed as additives.
- Zhang, Zi-Yu,Liu, Zhi-Yun,Guo, Rui-Ting,Zhao, Yu-Quan,Li, Xiang,Wang, Xiao-Chen
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supporting information
p. 4028 - 4032
(2017/03/27)
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- Synthesis of functionalized 2-isoxazolines as three-dimensional fragments for fragment-based drug discovery
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Abstract The design of new sp3 and spiro-enriched fragments has been achieved from 1,3-dipolar cycloaddition between alkenes and chloro-oximes. The selection of reagents was performed to afford a panel of 2-isoxazoline-containing fragments that show desirable three dimensional (3D) characteristics to allow the probing of biologically-relevant chemical space. Principal moments of inertia (PMI) were calculated to evaluate the 3D diversity. The resulting 3D fragments with suitable physicochemical properties, especially a good solubility, will be used to improve the hit rate of our fragment-based screening.
- Tran, Ngoc Chau,Dhondt, Heleen,Flipo, Marion,Deprez, Benoit,Willand, Nicolas
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supporting information
p. 4119 - 4123
(2015/08/03)
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- Application of [hydroxy(tosyloxy)iodo]benzene in the wittig-ring expansion sequence for the synthesis of β-benzocycloalkenones from α-benzocycloalkenones
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The conversion of α-benzocycloalkenones to homologous β-benzocycloalkenones containing six, seven and eight-membered rings is reported. This was accomplished via a Wittig olefination-oxidative rearrangement sequence using [hydroxy(tosyloxy)iodo]-benzene (HTIB) is the oxidant, that enables the synthesis of regioisomeric pairs of methyl-substituted β-benzocycloalkenones. The incorporation of carbon-13 at C-1 of the β-tetralone nucleus was also demonstrated. The Wittig-HTIB approach is a useful alternative to analogous sequences in which Tl(NO3) 3·3H2O or the Prevost combination (AgNO 3/I2) are employed in the oxidation step.
- Justik, Michael W.,Koser, Gerald F.
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p. 217 - 225
(2007/10/03)
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- BINAP-Ru(II) and BINAP-Rh(I)-catalyzed asymmetric hydrogenation of olefins without heteroatom-functionalities
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Asymmetric hydrogebation of 1,1'-disubstituted olefins which have no heteroatom functionalities to allow additional interactions with catalyst centers, have been investigated by use of Ru(II) and Rh(I) complexes of BINAP as catalysts.Enantioselectivities and the sense of asymmetric induction are highly dependent on the structure of substrates and the nature of catalysts.Hydrogenation of 1-methyleneindan (1a), a five-membered methylenecycloalkane, gave the highest optical yield (78percent) when Ru(OAc)2((R)-binap) was used as catalyst, while the use of the catalyst system 2/(R)-BINAP afforded the highest ees (71-82percent) for six-membered analogs, 1-methylenetetralin (4a) and its derivatives.In ciontrast, hydrogenation of seven-membered analog 7 and acyclic olefins 10 resulted in only moderate enantioselectivities by use of these catalysts.The BINAP-Ru(II) catalyzed hydrogenation exhibited a remarkable dependence of enantioselectivities on solvents, while a large anionic ligand effect was observed for the reaction with the BINAP-Rh(I) system.Based on these experimental results, mechanistic aspects of these asymmetric hydrogenation have been discussed.Keywords: Ruthenium; Rhodium; BINAP; Assymetric hydrogenation; Simple olefins; Catalysis
- Ohta, Tetsuo,Ikegami, Hiroshi,Miyake, Tsutomu,Takaya, Hidemasa
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p. 169 - 176
(2007/10/02)
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