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991.
Guannan Wang Hai Huang Wengang Guo Chenxiao Qian Jianwei Sun 《Angewandte Chemie (International ed. in English)》2020,59(28):11245-11249
Skeletal reorganization is a type of fascinating transformations owing to their intriguing mechanisms and utility in complex molecule synthesis. However, only a limited amount of examples are known for most functional groups. Herein, we describe such an unusual process of oxetanes. In the presence of In(OTf)3 as catalyst, oxetane‐tethered anilines reacted unexpectedly to form 1,2‐dihydroquinolines. This process not only provides expedient access to dihydroquinolines, but also represents a new reaction of oxetane. Mechanistically, it is believed that the reaction proceeds through initial nitrogen attack rather than arene attack followed by a series of bond cleavage and formation events. Control experiments provided important insights into the mechanism. 相似文献
992.
Xu‐Shuang Han Xinqi Luan Hai‐Feng Su Jiao‐Jiao Li Shang‐Fu Yuan Zhen Lei Yong Pei Quan‐Ming Wang 《Angewandte Chemie (International ed. in English)》2020,59(6):2309-2312
An alkynyl‐protected gold nanocluster, Au22(tBuC≡C)18 ( 1 ), has been synthesized and its structure has been determined by single‐crystal X‐ray diffraction. The molecular structure consists of a Au13 cuboctahedron kernel and three [Au3(tBuC≡C)4] trimeric staples. The cluster 1 has strong luminescence in the solid state with a 15 % quantum yield, and it displays interesting thermochromic luminescence as revealed by temperature‐dependent emission spectra. The enhanced room‐temperature emission is characterized as thermally activated delayed fluorescence. 相似文献
993.
994.
Jinhu Wei Liangliang Wu Hai‐Xu Wang Xiting Zhang Chun‐Wai Tse Cong‐Ying Zhou Jie‐Sheng Huang Chi‐Ming Che 《Angewandte Chemie (International ed. in English)》2020,59(38):16561-16571
Reliable methods for enantioselective cis‐dihydroxylation of trisubstituted alkenes are scarce. The iron(II) complex cis‐α‐[FeII(2‐Me2‐BQPN)(OTf)2], which bears a tetradentate N4 ligand (Me2‐BQPN=(R,R)‐N,N′‐dimethyl‐N,N′‐bis(2‐methylquinolin‐8‐yl)‐1,2‐diphenylethane‐1,2‐diamine), was prepared and characterized. With this complex as the catalyst, a broad range of trisubstituted electron‐deficient alkenes were efficiently oxidized to chiral cis‐diols in yields of up to 98 % and up to 99.9 % ee when using hydrogen peroxide (H2O2) as oxidant under mild conditions. Experimental studies (including 18O‐labeling, ESI‐MS, NMR, EPR, and UV/Vis analyses) and DFT calculations were performed to gain mechanistic insight, which suggested possible involvement of a chiral cis‐FeV(O)2 reaction intermediate as an active oxidant. This cis‐[FeII(chiral N4 ligand)]2+/H2O2 method could be a viable green alternative/complement to the existing OsO4‐based methods for asymmetric alkene dihydroxylation reactions. 相似文献
995.
Pin Xu Peng‐Yu Chen Hai‐Chao Xu 《Angewandte Chemie (International ed. in English)》2020,59(34):14275-14280
Heteroarenes are structural motifs found in many bioactive compounds and functional materials. Dehydrogenative cross‐coupling of heteroarenes with aliphatic C?H bonds provides straightforward access to functionalized heteroarenes from readily available materials. Established methods employ stoichiometric chemical oxidants under conditions of heating or light irradiation. By merging electrochemistry and photochemistry, we have achieved efficient photoelectrochemical dehydrogenative cross‐coupling of heteroarenes and C(sp3)?H donors through H2 evolution, without the addition of metal catalysts or chemical oxidants. Mechanistically, the C(sp3)?H donor is converted to a nucleophilic carbon radical through H‐atom transfer with chlorine atom, which is produced by light irradiation of anodically generated Cl2 from Cl?. The carbon radical then undergoes radical substitution to the heteroarene to afford alkylated heteroarene products. 相似文献
996.
Hai‐Dong Xia Zhong‐Liang Li Qiang‐Shuai Gu Xiao‐Yang Dong Jia‐Heng Fang Xuan‐Yi Du Li‐Lei Wang Xin‐Yuan Liu 《Angewandte Chemie (International ed. in English)》2020,59(39):16926-16932
We describe a photoinduced copper‐catalyzed asymmetric radical decarboxylative alkynylation of bench‐stable N‐hydroxyphthalimide(NHP)‐type esters of racemic alkyl carboxylic acids with terminal alkynes, which provides a flexible platform for the construction of chiral C(sp3)?C(sp) bonds. Critical to the success of this process are not only the use of the copper catalyst as a dual photo‐ and cross‐coupling catalyst but also tuning of the NHP‐type esters to inhibit the facile homodimerization of the alkyl radical and terminal alkyne, respectively. Owing to the use of stable and easily available NHP‐type esters, the reaction features a broader substrate scope compared with reactions using the alkyl halide counterparts, covering (hetero)benzyl‐, allyl‐, and aminocarbonyl‐substituted carboxylic acid derivatives, and (hetero)aryl and alkyl as well as silyl alkynes, thus providing a vital complementary approach to the previously reported method. 相似文献
997.
Hai‐Long Qian Fan‐Lin Meng Cheng‐Xiong Yang Xiu‐Ping Yan 《Angewandte Chemie (International ed. in English)》2020,59(40):17607-17613
Design of stable adsorbents for selective gold recovery with large capacity and fast adsorption kinetics is of great challenge, but significant for the economy and the environment. Herein, we show the design and preparation of an irreversible amide‐linked covalent organic framework (COF) JNU‐1 via a building block exchange strategy for efficient recovery of gold. JNU‐1 was synthesized through the exchange of 4,4′‐biphenyldicarboxaldehyde (BA) in mother COF TzBA consisting of 4,4′,4′′‐(1,3,5‐triazine‐2,4,6‐triyl)trianiline (Tz) and BA with terephthaloyl chloride. The irreversible amide linked JNU‐1 gave good stability, unprecedented fast kinetics, excellent selectivity and outstanding adsorption capacity for gold recovery. X‐ray photoelectron spectroscopy along with thermodynamic study and quantum mechanics calculation reveals that the excellent performance of JNU‐1 for gold recovery results from the formation of hydrogen bonds C(N)?H???Cl and coordinate interaction of O and Au. The rational design of irreversible bonds as both inherent linkage and functional groups in COFs is a promising way to prepare stable COFs for diverse applications. 相似文献
998.
目的:观察伐昔洛韦(valacyclovir)联合微米光治疗28例带状疱疹的临床疗效.方法:将54例带状疱疹患者随机分为两组,试验组28例口服伐昔洛韦(商品名:维德思)1 000 mg,每日3次,共服7d后改为每次500 mg,每日3次,继续服用7d.同时皮肤照射微米光每日一次,共照射14 d.对照组26例口服阿昔洛韦,200 mg,每日5次,同样每日照射微米光,与试验组一致,共14 d.观察记录第1、3、5、7、10、14天时止疱、结痂、疼痛及不良反应,第14天根据评分表评定总疗效.结果:试验组痊愈率为82.1%,对照组为46.2%,差异有统计学意义(P<0.01),试验组有效率为96.4%,对照组为73.1% (P <0.05).全部患者无严重不良反应发生,疗程结束后查肝肾功能无明显改变.结论:伐昔洛韦(维德思)联合微米光能明显缩短带状疱疹病程、加快水疱干枯结痂、促进皮损愈合、减少神经痛的程度及持续时间,降低后遗神经痛的发生率. 相似文献
999.
目的:探讨椎弓根钉系统复位固定椎间植骨融合治疗多节段腰椎滑脱的临床价值和相关问题。方法:11例多节段腰椎滑脱患者,男6例,女5例,年龄43~58岁,平均52.5岁,均为L4、5椎体滑脱,采用后路椎弓根螺钉系统复位固定,椎管减压,神经根松解,椎间植骨融合手术。术前、术后行腰腿痛视觉模拟评分(VAS),使用Os-westry功能障碍指数(OD I)问卷调查表评价临床功能恢复情况,并通过影像学检查观察滑脱恢复情况、椎间孔高度、植骨融合情况综合评价临床疗效。结果:11例患者均获随访,随访时间1~5年,平均3年2个月,VAS评分术后(1.0±1.0)分及末次随访(1.0±0.5)分,较术前(8.0±1.5)分均有显著性差异(P<0.005);OD I术后(22.13±13.40)及末次随访(20.31±13.27),较术前(64.80±15.68)均有显著差异(P<0.005)。术后椎间隙、椎间孔高度术后较术前明显增高,无内固定松动或断钉断棒;所有病例复位满意,所有患者植骨融合良好,无假关节形成。结论:后路椎弓根钉系统复位固定,椎管减压,神经根松解,椎间植骨融合治疗多节段腰椎滑脱效果满意,该术式具有复位良好,固定牢靠,... 相似文献
1000.