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1.
Runze Mao Jonathan Balon Prof. Dr. Xile Hu 《Angewandte Chemie (International ed. in English)》2018,57(41):13624-13628
Alkyl aryl ethers are an important class of compounds in medicinal and agricultural chemistry. Catalytic C(sp3)?O cross‐coupling of alkyl electrophiles with phenols is an unexplored disconnection strategy to the synthesis of alkyl aryl ethers, with the potential to overcome some of the major limitations of existing methods such as C(sp2)?O cross‐coupling and SN2 reactions. Reported here is a tandem photoredox and copper catalysis to achieve decarboxylative C(sp3)?O coupling of alkyl N‐hydroxyphthalimide (NHPI) esters with phenols under mild reaction conditions. This method was used to synthesize a diverse set of alkyl aryl ethers using readily available alkyl carboxylic acids, including many natural products and drug molecules. Complementarity in scope and functional‐group tolerance to existing methods was demonstrated. 相似文献
2.
《中国化学》2017,35(10):1491-1500
In recent years, a methodology merging photoredox catalysis with organocatalysis termed “photoredox organocatalysis” has emerged to allow the direct, selective and efficient functionalization of the α /β ‐C of carbonyl compounds under mild reaction condition. In this review, photophysics background of photoredox catalysis is introduced, followed by a report on recent advances in direct α ‐ and β ‐functionalization of carbonyls with photoredox organocatalysis methodology. With this different reaction modes, valuable synthetic targets including different α /β ‐functionalized carbonyls are accessible. 相似文献
3.
One‐Pot Tandem Photoredox and Cross‐Coupling Catalysis with a Single Palladium Carbodicarbene Complex 下载免费PDF全文
Yu‐Cheng Hsu Vincent C.‐C. Wang Ka‐Chun Au‐Yeung Chung‐Yu Tsai Chun‐Chi Chang Bo‐Chao Lin Prof. Yi‐Tsu Chan Prof. Chao‐Ping Hsu Prof. Glenn P. A. Yap Prof. Titel Jurca Prof. Tiow‐Gan Ong 《Angewandte Chemie (International ed. in English)》2018,57(17):4622-4626
The combination of conventional transition‐metal‐catalyzed coupling (2 e? process) and photoredox catalysis (1 e? process) has emerged as a powerful approach to catalyze difficult cross‐coupling reactions under mild reaction conditions. Reported is a palladium carbodicarbene (CDC) complex that mediates both a Suzuki–Miyaura coupling and photoredox catalysis for C?N bond formation upon visible‐light irradiation. These two catalytic pathways can be combined to promote both conventional transition‐metal‐catalyzed coupling and photoredox catalysis to mediate C?H arylation under ambient conditions with a single catalyst in an efficient one‐pot process. 相似文献
4.
Dr. Qingqing Bu Dr. Rositha Kuniyil Zhigao Shen Dr. Elżbieta Gońka Prof. Dr. Lutz Ackermann 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(69):16450-16454
C−H hydroxylation of aryl acetamides and alkyl phenylacetyl esters was accomplished via challenging distal weak O-coordination by versatile ruthenium(II/IV) catalysis. The ruthenium(II)-catalyzed C−H oxygenation of aryl acetamides proceeded through C−H activation, ruthenium(II/IV) oxidation and reductive elimination, thus providing step-economical access to valuable phenols. The p-cymene-ruthenium(II/IV) manifold was established by detailed experimental and DFT-computational studies. 相似文献
5.
Merger of Visible Light Induced Oxidation and Enantioselective Alkylation with a Chiral Iridium Catalyst 下载免费PDF全文
Chuanyong Wang Yu Zheng Haohua Huo Philipp Röse Dr. Lilu Zhang Dr. Klaus Harms Prof. Dr. Gerhard Hilt Prof. Dr. Eric Meggers 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(20):7355-7359
A single chiral octahedral iridium(III) complex is used for visible light activated asymmetric photoredox catalysis. In the presence of a conventional household lamp and under an atmosphere of air, the oxidative coupling of 2‐acyl‐1‐phenylimidazoles with N,N‐diaryl‐N‐(trimethylsilyl)methylamines provides aminoalkylated products in 61–93 % yields with high enantiomeric excess (90–98 % ee). Notably, the iridium center simultaneously serves three distinct functions: as the exclusive source of chirality, as the catalytically active Lewis acid, and as a central part of the photoredox sensitizer. This conceptionally simple reaction Scheme may provide new avenues for the green synthesis of non‐racemic chiral molecules. 相似文献
6.
Combining Photoredox‐Catalyzed Trifluoromethylation and Oxidation with DMSO: Facile Synthesis of α‐Trifluoromethylated Ketones from Aromatic Alkenes 下载免费PDF全文
Ren Tomita Dr. Yusuke Yasu Dr. Takashi Koike Prof. Dr. Munetaka Akita 《Angewandte Chemie (International ed. in English)》2014,53(28):7144-7148
Trifluoromethylated ketones are useful building blocks for organic compounds with a trifluoromethyl group. A new and facile synthesis of ketones with a trifluoromethyl substituent in the α‐position proceeds through a one‐pot photoredox‐catalyzed trifluoromethylation–oxidation sequence of aromatic alkenes. Dimethyl sulfoxide (DMSO) serves as a key and mild oxidant under these photocatalytic conditions. Furthermore, an iridium photocatalyst, fac[Ir(ppy)3] (ppy=2‐phenylpyridine), turned out to be crucial for the present photoredox process. 相似文献
7.
Oxydifluoromethylation of Alkenes by Photoredox Catalysis: Simple Synthesis of CF2H‐Containing Alcohols 下载免费PDF全文
Yusuke Arai Ren Tomita Gaku Ando Dr. Takashi Koike Prof. Dr. Munetaka Akita 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(4):1262-1265
We have developed a novel and simple protocol for the direct incorporation of a difluoromethyl (CF2H) group into alkenes by visible‐light‐driven photoredox catalysis. The use of fac‐[Ir(ppy)3] (ppy=2‐pyridylphenyl) photocatalyst and shelf‐stable Hu's reagent, N‐tosyl‐S‐difluoromethyl‐S‐phenylsulfoximine, as a CF2H source is the key to success. The well‐designed photoredox system achieves synthesis of not only β‐CF2H‐substituted alcohols but also ethers and an ester from alkenes through solvolytic processes. The present method allows a single‐step and regioselective formation of C(sp3)–CF2H and C(sp3)?O bonds from C=C moiety in alkenes, such as hydroxydifluoromethylation, regardless of terminal or internal alkenes. Moreover, this methodology tolerates a variety of functional groups. 相似文献
8.
Korkit Korvorapun Julia Struwe Rositha Kuniyil Agnese Zangarelli Anna Casnati Marjo Waeterschoot Lutz Ackermann 《Angewandte Chemie (International ed. in English)》2020,59(41):18103-18109
Ambient temperature ruthenium‐catalyzed C?H arylations were accomplished by visible light without additional photocatalysts. The robustness of the ruthenium‐catalyzed C?H functionalization protocol was reflected by a broad range of sensitive functional groups and synthetically useful pyrazoles, triazoles and sensitive nucleosides and nucleotides, as well as multifold C?H functionalizations. Biscyclometalated ruthenium complexes were identified as the key intermediates in the photoredox ruthenium catalysis by detailed computational and experimental mechanistic analysis. Calculations suggested that the in situ formed photoactive ruthenium species preferably underwent an inner‐sphere electron transfer. 相似文献
9.
Susan M. Stevenson Prof. Dr. Matthew P. Shores Prof. Dr. Eric M. Ferreira 《Angewandte Chemie (International ed. in English)》2015,54(22):6506-6510
The photooxidizing capabilities of selected CrIII complexes for promoting radical cation cycloadditions are described. These complexes have sufficiently long‐lived excited states to oxidize electron‐rich alkenes, thereby initiating [4+2] processes. These metal species augment the spectrum of catalysts explored in photoredox systems, as they feature unique properties that can result in differential reactivity from the more commonly employed ruthenium or iridium catalysts. 相似文献
10.
Zhenhua Zhang Tobias Hilche Daniel Slak Niels R. Rietdijk Ugochinyere N. Oloyede Robert A. Flowers Andreas Gansuer 《Angewandte Chemie (International ed. in English)》2020,59(24):9355-9359
Irradiation of Cp2TiCl2 with green light leads to electronically excited [Cp2TiCl2]*. This complex constitutes an efficient photoredox catalyst for the reduction of epoxides and for 5‐exo cyclizations of suitably unsaturated epoxides. To the best of our knowledge, our system is the first example of a molecular titanium photoredox catalyst. 相似文献
11.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(6):1632-1635
The first stereoconvergent cyclopropanation reaction by means of photoredox catalysis using diiodomethane as the methylene source is described. This transformation exhibits broad functional group tolerance and it is characterized by an excellent stereocontrol en route to trans ‐cyclopropanes regardless of whether E‐ or Z ‐styrene substrates were utilized. 相似文献
12.
Jing Qi Feng‐Lian Zhang Ji‐Kang Jin Qiang Zhao Bin Li Lin‐Xuan Liu Yi‐Feng Wang 《Angewandte Chemie (International ed. in English)》2020,59(31):12876-12884
Radical borylation using N‐heterocyclic carbene (NHC)‐BH3 complexes as boryl radical precursors has emerged as an important synthetic tool for organoboron assembly. However, the majority of reported methods are limited to reaction modes involving carbo‐ and/or hydroboration of specific alkenes and alkynes. Moreover, the generation of NHC‐boryl radicals relies principally on hydrogen atom abstraction with the aid of radical initiators. A distinct radical generation method is reported, as well as the reaction pathways of NHC‐boryl radicals enabled by photoredox catalysis. NHC‐boryl radicals are generated via a single‐electron oxidation and subsequently undergo cross‐coupling with the in‐situ‐generated radical anions to yield gem‐difluoroallylboronates. A photoredox‐catalyzed radical arylboration reaction of alkenes was achieved using cyanoarenes as arylating components from which elaborated organoborons were accessed. Mechanistic studies verified the oxidative formation of NHC‐boryl radicals through a single‐electron‐transfer pathway. 相似文献
13.
RuIII(OTf)SalophenCH2–NHSiO2–Fe: an efficient and magnetically recoverable catalyst for trimethylsilylation of alcohols and phenols with hexamethyldisilazane 下载免费PDF全文
Maryam Torki Shahram Tangestaninejad Valiollah Mirkhani Majid Moghadam Iraj Mohammadpoor‐Baltork 《应用有机金属化学》2014,28(4):304-309
Efficient trimethylsilylation of alcohols and phenols with hexamethyldisilazane (HMDS) catalyzed by ruthenium(III) complex of chloromethylated Salophen supported on nanomagnetic materials is reported. First, the iron nanomagnets were silica coated, functionalized with amine and then ruthenium CM‐Salophen was successfully bonded to their surface. The catalyst, RuIII(OTf)SalophenCH2–NHSiO2–Fe, was characterized by elemental analysis, FT‐IR and UV–visible spectroscopic techniques, transmission electron microscopy and inductively coupled plasma (ICP). The RuIII(OTf)SalophenCH2–NHSiO2–Fe catalyzed trimethylsilylation of primary and secondary alcohols as well as phenols, and the corresponding TMS ethers were obtained in high yields and short reaction times at room temperature. This new heterogenized trimethylsilylation catalyst is easily recovered with a magnet and showed no appreciable loss of activity even after five consecutive runs. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
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15.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(51):16536-16540
The coupling of ortho ‐ and para ‐phenols with secondary and tertiary boronic esters has been explored. In the case of para ‐substituted phenols, after reaction of a dilithio phenolate species with a boronic ester, treatment with Ph3BiF2 or Martin's sulfurane gave the coupled product with complete enantiospecificity. The methodology was applied to the synthesis of the broad spectrum antibacterial natural product (−)‐4‐(1,5‐dimethylhex‐4‐enyl)‐2‐methyl phenol. For ortho ‐substituted phenols, initial incorporation of a benzotriazole on the phenol oxygen atom was required. Subsequent ortho ‐lithiation and borylation gave the coupled product, again with complete stereospecificity. 相似文献
16.
Visible‐Light‐Induced Photoredox Catalysis of Dye‐Sensitized Titanium Dioxide: Selective Aerobic Oxidation of Organic Sulfides 下载免费PDF全文
Dr. Xianjun Lang Prof. Jincai Zhao Prof. Xiaodong Chen 《Angewandte Chemie (International ed. in English)》2016,55(15):4697-4700
TiO2 photoredox catalysis has recently attracted much interest for use in performing challenging organic transformations under mild reaction conditions. However, the reaction scheme is hampered by the fact that TiO2 can only be excited by UV light of wavelengths λ shorter than 385 nm. One promising strategy to overcome this issue is to anchor an organic, preferably metal‐free dye onto the surface of TiO2. Importantly, we observed that the introduction of a catalytic amount of the redox mediator TEMPO [(2,2,6,6‐tetramethylpiperidin‐1‐yl)oxyl] ensured the stability of the anchored dye, alizarin red S, thereby resulting in the selective oxidation of organic sulfides with O2. This result affirms the essential role of the redox mediator in enabling the organic transformations by visible‐light photoredox catalysis. 相似文献
17.
A series of ruthenium carbene catalysts containing 2‐sulfidophenolate bidentate ligand with an ortho‐substituent next to the oxygen atom were synthesized. The molecular structure of ruthenium carbene complex containing 2‐isopropyl‐6‐sulfidophenolate ligand was confirmed through single crystal X‐ray diffraction. An oxygen atom can be found in the opposite position of the N‐heterocyclic carbene (NHC) based on the steric hindrance and strong trans‐effects of the NHC ligand. The ruthenium carbene catalyst can catalyze ring‐opening metathesis polymerization (ROMP) reaction of norbornene with high activity and Z‐selectivity and cross metathesis (CM) reactions of terminal alkenes with (Z)‐but‐2‐ene‐1,4‐diol to give Z‐olefin products (Z/E ratios, 70:30–89:11) in low yields (13%–38%). When AlCl3 was added into the CM reactions, yields (51%–88%) were considerably improved and process becomes highly selective for E‐olefin products (E/Z ratios, 79:21–96:4). Similar to other ruthenium carbene catalysts, these new complexes can tolerate different functional groups. 相似文献
18.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(47):15327-15331
The para ‐selective C−H alkylation of aniline derivatives furnished with a pyrimidine auxiliary is herein reported. This reaction is proposed to take place via an N−H‐activated cyclometalate formed in situ. Experimental and DFT mechanistic studies elucidate a dual role of the ruthenium catalyst. Here the ruthenium catalyst can undergo cyclometalation by N−H metalation (as opposed to C−H metalation in meta ‐selective processes) and form a redox active ruthenium species, to enable site‐selective radical addition at the para position. 相似文献
19.
Immobilization and Continuous Recycling of Photoredox Catalysts in Ionic Liquids for Applications in Batch Reactions and Flow Systems: Catalytic Alkene Isomerization by Using Visible Light 下载免费PDF全文
M. Sc. David C. Fabry B. Sc. Meria A. Ronge Prof. Dr. Magnus Rueping 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(14):5350-5354
A catalytic (E)‐ to (Z)‐isomerization of olefins using a photoredox catalyst under mild reaction conditions is presented. A variety of (Z)‐alkenes can be prepared in the presence of visible light. A new reaction system allows an easy and efficient scale‐up, as well as a continuous flow process in which the photocatalyst is immobilized in an ionic liquid and continuously recycled by simple phase separation. 相似文献
20.
anti‐Markovnikov Hydroamination of Alkenes Catalyzed by a Two‐Component Organic Photoredox System: Direct Access to Phenethylamine Derivatives 下载免费PDF全文
Tien M. Nguyen Namita Manohar Prof. David A. Nicewicz 《Angewandte Chemie (International ed. in English)》2014,53(24):6198-6201
Disclosed herein is a general catalytic system for the intermolecular anti‐Markovnikov hydroamination of alkenes. By using an organocatalytic photoredox system, α‐ and β‐substituted styrenes as well as aliphatic alkenes undergo anti‐Markovnikov hydroamination. Heterocyclic amines were also successfully employed as nitrogen nucleophiles, thus providing a direct route to heterocyclic motifs common in medicinal agents. 相似文献