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1.
Pictet–Spengler Synthesis of Quinoline‐Fused Porphyrins and Phenanthroline‐Fused Diporphyrins 下载免费PDF全文
Dr. Ke Gao Norihito Fukui Seok II Jung Prof. Dr. Hideki Yorimitsu Prof. Dr. Dongho Kim Prof. Dr. Atsuhiro Osuka 《Angewandte Chemie (International ed. in English)》2016,55(42):13038-13042
Doubly and quadruply quinoline‐fused porphyrins were effectively synthesized through a reaction sequence consisting of Suzuki–Miyaura coupling of β‐borylated porphyrins with 2‐iodoaniline and subsequent Pictet–Spengler cyclization. These quinoline‐fused porphyrins display red‐shifted absorption bands and higher electron‐accepting abilities. This synthetic protocol also allowed the synthesis of phenanthroline‐fused porphyrin dimers, which bound either a NiII or ZnII cation. The resultant metal complexes displayed further red shifted absorption spectra and molecular twists to effect an almost perpendicular arrangement of the two porphyrins. 相似文献
2.
Palladium(II)/Brønsted Acid‐Catalyzed Enantioselective Oxidative Carbocyclization–Borylation of Enallenes 下载免费PDF全文
Tuo Jiang Dr. Teresa Bartholomeyzik Dr. Javier Mazuela Jochen Willersinn Prof. Dr. Jan‐E. Bäckvall 《Angewandte Chemie (International ed. in English)》2015,54(20):6024-6027
An enantioselective oxidative carbocyclization–borylation of enallenes that is catalyzed by palladium(II) and a Brønsted acid was developed. Biphenol‐type chiral phosphoric acids were superior co‐catalysts for inducing the enantioselective cyclization. A number of chiral borylated carbocycles were synthesized in high enantiomeric excess. 相似文献
3.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(6):1517-1521
An iridium/bipyridine‐catalyzed ortho ‐selective C−H borylation of aryl sulfides was developed. High ortho ‐selectivity was achieved by a Lewis acid–base interaction between a boryl group of the ligand and a sulfur atom of the substrate. This is the first example of a catalytic and regioselective C−H transformation controlled by a Lewis acid–base interaction between a ligand and a substrate. The C−H borylation reaction could be conducted on a gram scale, and with a bioactive molecule as a substrate, demonstrating its applicability to late‐stage regioselective C−H borylation. A bioactive molecule was synthesized from an ortho ‐borylated product by converting the boryl and methylthio groups of the product. 相似文献
4.
Copper‐Catalyzed Borocarbonylative Coupling of Internal Alkynes with Unactivated Alkyl Halides: Modular Synthesis of Tetrasubstituted β‐Borylenones 下载免费PDF全文
Li‐Jie Cheng Neal P. Mankad 《Angewandte Chemie (International ed. in English)》2018,57(32):10328-10332
Reported is a general procedure to synthesize tetrasubstituted enones, which are borylated in the β‐position, using a copper‐catalyzed four‐component coupling reaction of simple chemical feedstocks: internal alkynes, alkyl halides, bis(pinacolato)diboron (B2pin2), and CO. A broad scope of highly functionalized β‐borylated enones, a largely unknown class of organic compounds, can be accessed efficiently using this method. The synthesis of all‐carbon tetrasubstituted enones was realized by employing the β‐borylated enone unit, without purification, in a Suzuki–Miyaura coupling. The utility of the method was further demonstrated by various transformations, including halogenation, oxidation, and protodeboration, of the corresponding reduced oxaborole species to provide densely substituted allylic alcohol and ketone products. 相似文献
5.
Timothy E. Hurst Dr. Todd K. Macklin Dr. Maike Becker Eduard Hartmann Wolfgang Kügel Jean‐Christophe Parisienne‐La Salle Andrei S. Batsanov Dr. Todd B. Marder Prof. Dr. Victor Snieckus Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(27):8155-8161
Systematic studies are presented demonstrating the complementarity of directed ortho metalation (DoM) and Ir‐catalyzed strategies for the provision of borylated aromatics and their subsequent Suzuki–Miyaura coupling reactions. A new concept, the use of the TMS group, readily introduced by DoM, as a latent regiodirective moiety to overcome the otherwise problematic production of isomeric borylated product mixtures is presented. Additional electrophile‐induced ipso‐deborylation and DoM reactions of the Bpin products are described. 相似文献
6.
Dr. Youai Qiu Bin Yang Dr. Can Zhu Prof. Dr. Jan‐E. Bäckvall 《Angewandte Chemie (International ed. in English)》2016,55(22):6520-6524
A highly efficient palladium‐catalyzed oxidative borylation of enallenes was developed for the selective formation of cyclobutene derivatives and fully‐substituted alkenylboron compounds. Cyclobutenes are formed as the exclusive products in MeOH in the presence of H2O and Et3N, whereas the use of AcOH leads to alkenylboron compounds. Both reactions showed a broad substrate scope and good tolerance for various functional groups, including carboxylic acid ester, free hydroxy, imide, and alkyl groups. Furthermore, transformations of the borylated products were conducted to show their potential applications. 相似文献
7.
Guangzhu Wang Xinyi Liang Lili Chen Qian Gao Jian‐Guo Wang Panke Zhang Qian Peng Senmiao Xu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(24):8271-8275
The regioselective hydroboration of aliphatic internal alkenes remains a great challenge. Reported herein is an iridium‐catalyzed hydroboration of aliphatic internal alkenes, providing distal‐borylated products in good to excellent yields with high regioselectivity (up to 99:1). We also demonstrate that the C?B bond of the distal‐borylated product can be readily converted into other functional groups. DFT calculations indicate that the reaction proceeds through an unexpected IrIII/IrV cycle. 相似文献
8.
New electroluminescent materials of 1,3,4‐oxadiazole–1,2,3‐triazole and 1,3,4‐oxadiazole–1,2,3‐triazole–pyridine hybrid derivatives were synthesized and characterized. Following spectroscopic studies and characterization of their electronic properties, 1,3,4‐oxadiazole–1,2,3‐triazole hybrids and 1,3,4‐oxadiazole–1,2,3‐triazole–pyridine derivatives were found to be potentially efficient blue electroluminescent materials. © 2006 Wiley Periodicals, Inc. Heteroatom Chem 17:322–328, 2006; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20210 相似文献
9.
Liang Ling Yuan He Xue Zhang Meiming Luo Xiaoming Zeng 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(20):6626-6630
We herein report the hydrogenation of substituted aryl‐ and heteroaryl boronate esters for the selective synthesis of cis‐substituted borylated cycloalkanes and saturated heterocycles. A cyclic (alkyl)(amino)carbene‐ligated rhodium complex with two dimethyl groups at the ortho‐alkyl scaffold of the carbene showed high reactivity in promoting the hydrogenation, thereby enabling the hydrogenation of (hetero)arenes with retention of the synthetically valuable boronate group. This process constitutes a clean, atom‐economic, as well as chemo‐ and stereoselective route for the generation of cis‐configured, diversely substituted borylated cycloalkanes and saturated heterocycles that are usually elusive and difficult to prepare. 相似文献
10.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(1):360-364
BCl3‐induced borylative cyclization of aryl‐alkynes possessing ortho‐EMe (E=S, O) groups represents a simple, metal‐free method for the formation of C3‐borylated benzothiophenes and benzofurans. The dichloro(heteroaryl)borane primary products can be protected to form synthetically ubiquitous pinacol boronate esters or used in situ in Suzuki–Miyaura cross couplings to generate 2,3‐disubstituted heteroarenes from simple alkyne precursors in one pot. In a number of cases alkyne trans‐haloboration occurs alongside, or instead of, borylative cyclization and the factors controlling the reaction outcome are determined. 相似文献
11.
Wen‐Hao Guo Qiao‐Qiao Min Ji‐Wei Gu Prof. Dr. Xingang Zhang 《Angewandte Chemie (International ed. in English)》2015,54(31):9075-9078
An ortho‐selective C? F bond borylation between N‐heterocycle‐substituted polyfluoroarenes and Bpin‐Bpin with simple and commercially available [Rh(cod)2]BF4 as a catalyst is now reported. The reaction proceeds under mild reaction conditions with high efficiency and broad substrate scope, even toward monofluoroarene, thus providing a facile access to a wide range of borylated fluoroarenes that are useful for photoelectronic materials. Preliminary mechanistic studies reveal that a RhIII/V catalytic cycle via a key intermediate rhodium(III) hydride complex [(H)RhIIILn(Bpin)] may be involved in the reaction. 相似文献
12.
Synthesis of Previously Inaccessible Borylated Heterocycle Motifs Using Novel Boron‐Containing Amphoteric Molecules 下载免费PDF全文
Dr. Piera Trinchera Victoria B. Corless Prof. Dr. Andrei K. Yudin 《Angewandte Chemie (International ed. in English)》2015,54(31):9038-9041
The photoredox‐organocatalyzed α‐alkylation of the α‐MIDA boryl aldehyde with a range of α‐bromoketones resulted in the first examples of boron‐containing 1,4‐dicarbonyl compounds. These novel trifunctional amphoteric molecules, which bear an additional, strategically placed electrophilic site compared to the starting amphoteric α‐boryl aldehyde, were subjected to double‐condensation reactions in the presence of various nucleophiles. As a result, a variety of synthetically challenging 3‐borylated pyrroles and furans and 4‐borylated pyridazines were generated. The borylated regioisomers accessible with this condensation‐based strategy are distinctly different from those arising from the well‐known lithiation and C? H activation processes. 相似文献
13.
Paul Kautny Dorian Bader Dr. Berthold Stöger Prof. Dr. Georg A. Reider Prof. Dr. Johannes Fröhlich Dr. Daniel Lumpi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(52):18887-18898
To shed light on intramolecular charge‐transfer phenomena in 1,2,3‐triazole‐linked materials, a series of 1,2,3‐triazole‐linked push–pull chromophores were prepared and studied experimentally and computationally. Investigated modifications include variation of donor and/or acceptor strength and linker moiety as well as regioisomers. Photophysical characterization of intramolecular charge‐transfer features revealed ambipolar behavior of the triazole linker, depending on the substitution position. Furthermore, non‐centrosymmetric materials were subjected to second‐harmonic generation measurements, which revealed the high nonlinear optical activity of this class of materials. 相似文献
14.
Dr. Abdelkrim El Kadib Prof. Mosto Bousmina 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(27):8264-8277
Recently, organic–inorganic hybrid materials have attracted tremendous attention thanks to their outstanding properties, their efficiency, versatility and their promising applications in a broad range of areas at the interface of chemistry and biology. This article deals with a new family of surface‐reactive organic–inorganic hybrid materials built from chitosan microspheres. The gelation of chitosan (a renewable amino carbohydrate obtained by deacetylation of chitin) by pH inversion affords highly dispersed fibrillar networks shaped as self‐standing microspheres. Nanocasting of sol–gel processable monomeric alkoxides inside these natural hydrocolloids and their subsequent CO2 supercritical drying provide high‐surface‐area organic–inorganic hybrid materials. Examples including chitosan–SiO2, chitosan–TiO2, chitosan–redox‐clusters and chitosan–clay‐aerogel microspheres are described and discussed on the basis of their textural and structural properties, thermal and chemical stability and their performance in catalysis and adsorption. 相似文献
15.
Synthesis of Stereodefined Borylated Dendralenes through Copper‐Catalyzed Allylboration of Alkynes 下载免费PDF全文
Eva Rivera‐Chao Dr. Martín Fañanás‐Mastral 《Angewandte Chemie (International ed. in English)》2018,57(31):9945-9949
An efficient method to access diversely substituted borylated dendralenes from simple and readily available materials is reported. This method is based on a multicomponent copper‐catalyzed allylboration of alkynes with diboron and a 1,4‐dibromo‐2‐butene which provides bromo‐ and boron‐substituted skipped dienes with a remarkable chemo‐, stereo‐, and regioselectivity. These products can be easily transformed into dendralenic organoboronates, which display an extremely versatile reactivity as demonstrated by novel selective transformations. 相似文献
16.
Catalyst‐Free Formal Thioboration to Synthesize Borylated Benzothiophenes and Dihydrothiophenes 下载免费PDF全文
Darius J. Faizi Ashlee J. Davis Fiach B. Meany Prof. Dr. Suzanne A. Blum 《Angewandte Chemie (International ed. in English)》2016,55(46):14286-14290
The first ring‐forming thioboration reaction of C?C π bonds is reported. This catalyst‐free method proceeds in the presence of a commercially available external electrophilic boron source (B‐chlorocatecholborane) in good to high yields. The method is scalable and tolerates a variety of functional groups that are intolerant of other major borylation methods. The resulting borylated benzothiophenes participate in a variety of in situ derivatization reactions, showcasing that these borylated intermediates do not need to be isolated prior to downstream functionalization. This methodology has been extended to the synthesis of borylated dihydrothiophenes. Mechanistic experiments suggest that the operative mechanistic pathway is through boron‐induced activation of the alkyne followed by electrophilic cyclization, as opposed to S?B σ bond formation, providing a mechanistically distinct pathway to the thioboration of C?C π bonds. 相似文献
17.
Synthesis of Nanoporous Carbon–Cobalt‐Oxide Hybrid Electrocatalysts by Thermal Conversion of Metal–Organic Frameworks 下载免费PDF全文
Dr. Watcharop Chaikittisilp Dr. Nagy L. Torad Dr. Cuiling Li Dr. Masataka Imura Dr. Norihiro Suzuki Dr. Shinsuke Ishihara Prof. Dr. Katsuhiko Ariga Prof. Dr. Yusuke Yamauchi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(15):4217-4221
Nanoporous carbon–cobalt‐oxide hybrid materials are prepared by a simple, two‐step, thermal conversion of a cobalt‐based metal–organic framework (zeolitic imidazolate framework‐9, ZIF‐9). ZIF‐9 is carbonized in an inert atmosphere to form nanoporous carbon–metallic‐cobalt materials, followed by the subsequent thermal oxidation in air, yielding nanoporous carbon–cobalt‐oxide hybrids. The resulting hybrid materials are evaluated as electrocatalysts for the oxygen‐reduction reaction (ORR) and the oxygen‐evolution reaction (OER) in a KOH electrolyte solution. The hybrid materials exhibit similar catalytic activity in the ORR to the benchmark, commercial, Pt/carbon black catalyst, and show better catalytic activity for the OER than the Pt‐based catalyst. 相似文献
18.
Ekkehard Müh Markus Stieger Joachim E. Klee Holger Frey Rolf Mülhaupt 《Journal of polymer science. Part A, Polymer chemistry》2001,39(24):4274-4282
Organic–inorganic hybrid materials were prepared by a convenient two‐step curing procedure based on sol–gel condensation and subsequent photopolymerization. Novel bismethacrylate‐based hybrid monomers with pendant, condensable alkoxysilane groups were prepared by Michael addition and possessed number‐average molecular weights between 580 and 1600 g/mol. The formation of inorganic networks by sol–gel condensation of the alkoxysilane groups in the presence of aqueous methacrylic acid was monitored with rheological measurements. The condensation conversion was monitored with solid‐state 29Si cross‐polarization/magic‐angle spinning NMR spectroscopy. Subsequent photopolymerization led to organic–inorganic hybrid networks and low volume shrinkage, ranging from 4.2 to 8.3%, depending on the molecular weight of the hybrid monomer applied. Highly filled composite materials with glass filler fractions greater than 75% showed attractive mechanical properties with Young's moduli of 2700–6200 MPa. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 4274–4282, 2001 相似文献
19.
Design of donor–acceptor–donor (D–A–D) type small molecule donor materials with efficient photovoltaic parameters 下载免费PDF全文
Muhammad Irfan Javed Iqbal Sana Sadaf Bertil Eliasson Usman Ali Rana Salah Ud‐din Khan Khurshid Ayub 《International journal of quantum chemistry》2017,117(10)
Four Donor–Acceptor–Donor (D–A–D) type of donor molecules (M1‐M4) with triphenylamine (TPA) as donor moiety, thiophene as bridge, and thiazolothiazole as acceptor unit were designed and its photovoltaic parameters were equated with reference molecule “R.” DFT functional CAM‐B3LYP/6‐31G (d,p) was found best for geometry optimization and TD‐CAM‐B3LYP/6‐31G (d,p) was found suitable for excited state calculations. Among designed donor molecules, M4 manifests suitable lowest band gap of 4.73 eV, frontier molecular orbital energy levels as well as distinctive broad absorption of 455.3 nm due to the stronger electron withdrawing group. The electron‐withdrawing substituents contribute to red shifts of absorption spectra and better stabilities for designed molecules. The theoretically determined reorganization energies of designed donor molecules suggested excellent charge mobility property. The lower λe values in comparison with λh illustrated that these four donor materials would be ideal for electron transfer and M4 would be best amongst the investigated molecules with lowest λe of 0.0177. Furthermore, the calculated Voc of M4 is 2.04 V with respect to PC60BM (phenyl‐C61‐butyric acid methyl ester). This study revealed that the designed donor materials are suitable and recommended for high performance organic solar cell devices. 相似文献
20.
Licheng Wu Feilong Li Yutao Rao Bin Wen Ling Xu Mingbo Zhou Takayuki Tanaka Atsuhiro Osuka Jianxin Song 《Angewandte Chemie (International ed. in English)》2019,58(24):8124-8128
A reaction sequence of regioselective peripheral bromination, Suzuki–Miyaura coupling with 2‐borylated thiophene or pyrrole, and oxidative ring‐closure with FeCl3 allowed the synthesis of heterole‐fused earring porphyrins 4Pd and 9Pd from the parent earring porphyrin 1 . Differently pyrrole‐fused porphyrins 5H and 6H and their PdII complexes 5Pd and 6Pd were also synthesized. The structures of 4Pd , 5H, 6Pd , and 8Pd have been revealed by X‐ray analysis to be slightly twisted owing to constraints imposed by heterole‐fused structures. 5Pd exhibits an intensified band at 1505 nm, while 4Pd and 9Pd display small but remarkably red‐shifted absorption bands reaching around 2200 nm. 相似文献