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991.
Xu‐Jie Qin Tyler J. Rauwolf Pan‐Pan Li Hui Liu James McNeely Yan Hua Hai‐Yang Liu John A. Porco 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(13):4335-4340
Rhodomyrtusials A–C, the first examples of triketone‐sesquiterpene meroterpenoids featuring a unique 6/5/5/9/4 fused pentacyclic ring system were isolated from Rhodomyrtus tomentosa, along with several biogenetically‐related dihydropyran isomers. Two bis‐furans and one dihydropyran isomer showed acetylcholinesterase (AChE) inhibitory activity. Structures of the isolates were unambiguously established by a combination of spectroscopic data, ECD analysis, and total synthesis. Bioinspired total syntheses of six isolates were achieved in six steps utilizing a reactive enetrione intermediate generated in situ from a readily available hydroxy‐endoperoxide precursor. 相似文献
992.
Xing Wei Meng‐Jiao Zhu Zhe Cheng Mengjeu Lee Hong Yan Changsheng Lu Jing‐Juan Xu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(10):3194-3198
The aggregation‐induced electrochemiluminescence (AIECL) of carboranyl carbazoles in aqueous media was investigated for the first time. Quantum yields, morphologies, and particle sizes were observed to determine the electrochemiluminescence (ECL) performance of these aggregated organic dots (ODs). All compounds exhibit much higher ECL stability and intensity than the carborane‐free compound, demonstrating the essential role of the carboranyl motif. Moreover, the results of cyclic voltammetry (CV) suggest that oxidation/reduction reactions take place at the carboranyl motif. The excited states of ODs were proposed to be generated by the mechanism of surface state transitions. More importantly, these compounds show a reductive–oxidative mechanism in contrast to other organic materials that show oxidative–reductive mechanisms. Our experiments and data have established the relation between AIE organic structures and ECL properties that has a strong potential for biological and diagnostic applications. 相似文献
993.
Chuan He Jun Xuan Peirong Rao Pei‐Pei Xie Xin Hong Xufeng Lin Hanfeng Ding 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(15):5154-5158
A concise and divergent approach for the total syntheses of four cembrane diterpenoids, namely (+)‐sarcophytin, (+)‐chatancin, (?)‐3‐oxochatancin, and (?)‐pavidolide B, has been developed, and it also led to the structural revision of (?)‐isosarcophytin. The key steps of the strategy feature a double Mukaiyama Michael addition/elimination, a Helquist annulation, two substrate‐controlled facial‐selective hydrations, and a pinacol rearrangement. The described syntheses not only achieved these natural products in an efficient manner, but also provided insight into the biosynthetic relationship between the two different skeletons. 相似文献
994.
Xiao Liang Lei Shi Yipu Liu Hui Chen Rui Si Wensheng Yan Qi Zhang Guo‐Dong Li Li Yang Xiaoxin Zou 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(23):7713-7717
Simultaneous realization of improved activity, enhanced stability, and reduced cost remains a desirable yet challenging goal in the search of oxygen evolution electrocatalysts in acid. Herein we report iridium‐containing strontium titanates (Ir‐STO) as active and stable, low‐iridium perovskite electrocatalysts for the oxygen evolution reaction (OER) in acid. The Ir‐STO contains 57 wt % less iridium relative to the benchmark catalyst IrO2, but it exhibits more than 10 times higher catalytic activity for OER. It is shown to be among the most efficient iridium‐based oxide electrocatalysts for OER in acid. Theoretical results reveal that the incorporation of iridium dopants in the STO matrix activates the intrinsically inert titanium sites, strengthening the surface oxygen adsorption on titanium sites and thereby giving nonprecious titanium catalytic sites that have activities close to or even better than iridium sites. 相似文献
995.
996.
Qiang Cheng Jia‐Hao Xie Yue‐Cheng Weng Shu‐Li You 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(17):5795-5799
Dearomatization of anthranils with vinylcyclopropanes (VCPs) by Pd‐catalyzed [4+3] cyclization reaction has been realized. In the presence of a catalytic amount of borane as an activator, bridged cyclic products were obtained in good to excellent yields with excellent stereoselectivities. By introducing a chiral PHOX ligand ( L5 ), asymmetric dearomatization reactions of anthranils with vinylcyclopropanes proceeded with excellent enantioselectivity. Borane plays a key role for the reactivity, likely owing to the formation of a borane–anthranil complex which has been confirmed by NMR experiments. 相似文献
997.
Jian‐Qiang Huang Chun‐Yu Ho 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(17):5758-5762
A cross‐hydroalkenylation/rearrangement cascade (HARC), using a cyclopropene and alkyne as substrate pairs, was achieved for the first time by using new [(NHC)Ni(allyl)]BArF catalysts (NHC=N‐heterocyclic carbenes). By controlling the (NHC)NiIIH relative insertion reactivity with cyclopropene and alkyne, a broad scope of cyclopentadienes was obtained with highly selectively. The structural features of the new (NHC)NiII catalyst were important for the success of the reaction. The mild reaction conditions employed may serve as an entry for exploring (NHC)NiII‐assisted vinylcyclopropane rearrangement reactivity. 相似文献
998.
Lu‐Lu Li Du Ding Jin Song Zhi‐Yong Han Liu‐Zhu Gong 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(23):7729-7733
A general strategy for the design of asymmetric cascade reactions using readily available halides and carbon monoxide (CO) as substrates is developed. The key is the catalytic generation of C1‐ammonium enolates for the subsequent asymmetric cascade reactions through the combination of palladium‐catalyzed carbonylation and chiral Lewis base catalysis. Utilizing this strategy, we have established asymmetric formal [1+1+4] and [1+1+2] reactions to afford chiral dihydropyridones and β‐lactams with high yields and high enantio‐ and diastereoselectivities. 相似文献
999.
Yinjun Xie Peng Hu Yehoshoa Ben‐David David Milstein 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(15):5159-5163
A novel liquid organic hydrogen carrier (LOHC) system, with a high theoretical hydrogen capacity, based on the unpresented hydrogenation of ethylene urea to ethylenediamine and methanol, and its reverse dehydrogenative coupling, was established. For the dehydrogenation only a small amount of solvent is required. This system is rechargeable, as the H2‐rich compounds could be regenerated by hydrogenation of the resulting dehydrogenation mixture. Both directions for hydrogen loading and unloading were achieved using the same catalyst, under relatively mild conditions. Mechanistic studies reveal the likely pathway for H2‐lean compounds formation. 相似文献
1000.
Daniel Pinchuk Yosi Kratish Jomon Mathew Lieby Zborovsky Dmitry Bravo‐Zhivotovskii Boris Tumanskii Yitzhak Apeloig 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(22):7513-7517
The first two persistent silenyl radicals (R2C=Si.?R), with a half‐life (t1/2) of about 30 min, were generated and characterized by electron paramagnetic resonance (EPR) spectroscopy. The large hyperfine coupling constants (hfccs) (a(29Siα)=137.5–148.0 G) indicate that the unpaired electron has substantial s character. DFT calculations, which are in good agreement with the experimentally observed hfccs, predict a strongly bent structure (?C=Si?R=134.7–140.7°). In contrast, the analogous vinyl radical, R2C=C.?R (t1/2≈3 h), exhibits a small hfcc (a(13Cα)=26.6 G) and has a nearly linear geometry (?C=C?R=168.7°). 相似文献