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1.
Hua-Dong He Dr. Ravi Chitrakar Zhi-Wei Cao Dao-Ming Wang Li-Qin She Peng-Gang Zhao Dr. Yichen Wu Prof. Dr. Yuan-Qing Xu Dr. Zhong-Yan Cao Prof. Dr. Peng Wang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2024,136(1):e202313336
The precise control of the regioselectivity in the transition metal-catalyzed migratory hydrofunctionalization of alkenes remains a big challenge. With a transient ketimine directing group, the nickel-catalyzed migratory β-selective hydroarylation and hydroalkenylation of alkenyl ketones has been realized with aryl boronic acids using alkyl halide as the mild hydride source for the first time. The key to this success is the use of a diphosphine ligand, which is capable of the generation of a Ni(II)-H species in the presence of alkyl bromide, and enabling the efficient migratory insertion of alkene into Ni(II)-H species and the sequent rapid chain walking process. The present approach diminishes organosilanes reductant, tolerates a wide array of complex functionalities with excellent regioselective control. Moreover, this catalytic system could also be applied to the migratory hydroarylation of alkenyl azahetereoarenes, thus providing a general approach for the preparation of 1,2-aryl heteroaryl motifs with wide potential applications in pharmaceutical discovery. 相似文献
2.
Binlin Zhao Zexian Li Yixiao Wu Yandong Wang Jiasheng Qian Yu Yuan Zhuangzhi Shi 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(28):9548-9552
A series of in situ formed alkenyl diboronate complexes from alkenyl Grignard reagents (commercially available or prepared from alkenyl bromides and Mg) with B2Pin2 (bis(pinacolato)diboron) react with diverse alkyl halides by a Ru photocatalyst to give various gem‐bis(boryl)alkanes. Alkyl radicals add efficiently to the alkenyl diboronate complexes, and the adduct radical anions undergo radical‐polar crossover, specifically, a 1,2‐boryl‐anion shift from boron to the α‐carbon sp2 center. This transformation shows good functional‐group compatibility and can serve as a powerful synthetic tool for late‐stage functionalization in complex compounds. Measurements of the quantum yield reveal that a radical‐chain mechanism is operative in which the alkenyl diboronates acts as reductive quencher for the excited state of the photocatalyst. 相似文献
3.
(E)- and (Z)-configured alpha-lithioalkenyl sulfoximines, which are available through lithiation of the corresponding alkenyl sulfoximines, undergo a anionic cross-coupling reaction (ACCR) with organocuprates with formation of the corresponding alkenyl cuprates and sulfinamide. The alkenyl cuprates can be trapped by electrophiles. The ACCR presumably proceeds via the formation of a higher-order sulfoximine-substituted alkenyl cuprate, which undergoes a 1,2-metal-ate rearrangement whereby the sulfoximine group acts as the nucleofuge. The parent (E)- and (Z)-configured alkenyl sulfoximines suffer upon treatment with an organocuprate a deprotonation at the alpha-position with formation of the corresponding alpha-cuprioalkenyl sulfoximines. These derivatives also enter into a similar ACCR with organocuprates. The ACCR of sulfoximines substituted homoallylic alcohols allows a stereoselective access to enantio- and diastereopure substituted homoallylic alcohols. 相似文献
4.
Songlin Zheng Zimin Chen Yuanyuan Hu Xiaoxiang Xi Zixuan Liao Weirong Li Prof. Dr. Weiming Yuan 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(41):18066-18072
A highly chemo- and regioselective intermolecular 1,2-aryl-aminoalkylation of alkenes by photoredox/nickel dual catalysis is described here. This three-component conjunctive cross-coupling is highlighted by its first application of primary alkyl radicals, which were not compatible in previous reports. The readily prepared α-silyl amines could be transferred to α-amino radicals by photo-induced single electron transfer step. The radical addition/cross-coupling cascade reaction proceeds under mild, base-free and redox-neutral conditions with good functional group tolerance, and importantly, provides an efficient and concise method for the synthesis of structurally valuable α-aryl substituted γ-amino acid derivatives motifs. 相似文献
5.
Yang Gao Simin Yang Minwei She Jianhong Nie Yanping Huo Qian Chen Xianwei Li Xiao-Qiang Hu 《Chemical science》2022,13(7):2105
We report a practical route for the synthesis of valuable 3-aryl anthranils from readily available anthranils and simple arenes by using the classical electrophilic aromatic substitution (EAS) strategy. This transformation goes through an electrophilic substitution and rearomatisation sequence by employing Tf2O as an effective activator. A wide range of arenes were compatible in this transformation, delivering various structurally diversified 3-aryl anthranils in good yields and high regioselectivity. In addition, a variety of readily available feedstocks such as olefins, alkenyl triflates, silyl enolethers, carbonyl compounds, thiophenols and thiols could also participate in the reaction to achieve the C3 alkenylation, alkylation and thioetherification of anthranils. Of note, the synthesized 3-aryl anthranils proved to be a highly robust platform to access a series of biologically active compounds, drug derivatives and organic optoelectronic materials.A practical route for the synthesis of valuable 3-aryl anthranils from readily available anthranils and simple arenes has been achieved through an electrophilic substitution and rearomatization sequence by employing Tf2O as an effective activator. 相似文献
6.
Dr. Yu-Ping He Rui Quan Xing-Zi Li Prof. Dr. Jieping Zhu Prof. Dr. Hua Wu 《Angewandte Chemie (International ed. in English)》2023,62(18):e202217954
An unprecedent asymmetric catalytic benzilic amide rearrangement for the synthesis of α,α-disubstituted piperazinones is reported. The reaction proceeds via a domino [4+1] imidazolidination/formal 1,2-nitrogen shift/1,2-aryl or alkyl migration sequence, employing readily available vicinal tricarbonyl compounds and 1,2-diamines as starting materials. This approach provides an efficient access to chiral C3-disubsituted piperazin-2-ones with high enantiocontrol, which are exceedingly difficult to access from the existing synthetic methodologies. The observed enantioselectivity was proposed to be controlled by dynamic kinetic resolution in the 1,2-aryl/alkyl migration step. The resulting densely functionalized products are versatile building blocks to bioactive natural products, drug molecules and their analogues. 相似文献
7.
A convenient method for the preparation of 2-aryl(or methyl)sulfanylbenzo[b]thiophenes has been developed. Thus, aryl 2-aryl(or methyl)sulfanylmethylsulfanylphenyl ketones, easily prepared from readily available aryl 2-sulfanylphenyl ketones or 2-chloro-5-nitrophenyl phenyl ketone, are treated with LDA in 1,2-dimethoxyethane (DME) to give 3-aryl-2-aryl(or methyl)sulfanylmethylsulfanyl-2,3-dihydrobenzo[b]thiophen-3-ols, which in turn were dehydrated with thionyl chloride to afford 3-aryl-2-aryl(or methyl)sulfanylbenzo[b]thiophenes in reasonable overall yields. 相似文献
8.
Prof. Dr. Wen-Jun Zhou Prof. Dr. Xu-Dong Wu Meng Miao Zhe-Hao Wang Liang Chen Si-Yi Shan Guang-Mei Cao Prof. Dr. Da-Gang Yu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(66):15052-15064
Over the past decades, organometallic complexes with precious elements, such as ruthenium and iridium, are widely used as visible-light photoredox catalysts. Recently, more and more complexes based on earth-abundant and inexpensive elements have been used as sensitizers in photochemistry. Although the photoexcited state lifetimes of iron complexes are typically shorter than those of traditional photosensitizers, the utilization of iron catalysts in photochemistry has sprung up owing to their abundance, low price, nontoxicity, and novel properties, including exhibiting ligand to metal charge transfer states. This concept focuses on recent advances in light-driven iron catalysis in organic transformations, including iron/photoredox dual catalysis, light-induced iron photoredox catalysis and light-induced generation of active iron catalysts. The prospect for the future of this field is also discussed. 相似文献
9.
Decarboxylative Aminomethylation of Aryl‐ and Vinylsulfonates through Combined Nickel‐ and Photoredox‐Catalyzed Cross‐Coupling
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Dr. Lulu Fan Jiaqi Jia Dr. Hong Hou Dr. Quentin Lefebvre Prof. Dr. Magnus Rueping 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(46):16437-16440
A mild approach for the decarboxylative aminomethylation of aryl sulfonates by the combination of photoredox and nickel catalysis through C?O bond cleavage is described for the first time. A wide range of aryl triflates as well as aryl mesylates, tosylates and alkenyl triflates afford the corresponding products in good to excellent yields. 相似文献
10.
11.
Devaraj Somasundaram Kalpattu K. Balasubramanain Bhagavathy Shanmugasundaram 《Tetrahedron letters》2019,60(11):764-767
The ring opening of α-d-1,2-anhydrohexapyranoses with phenols proceeded smoothly in ethyl acetate (neutral conditions) in the absence of metal ion catalysts or additives to stereoselectively furnish 1,2-cis-α-aryl glycosides as the major product and 1,2-trans-β-aryl glycosides as the minor product in good yields. Under similar conditions, this ring opening reaction with alcohols afforded exclusively β-alkyl glycosides in excellent yields. 相似文献
12.
Naohisa Nakagawa Prof. Dr. Takuji Hatakeyama Prof. Dr. Masaharu Nakamura 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(11):4257-4261
An iron‐catalyzed diboration reaction of alkynes with bis(pinacolato)diboron (B2pin2) and external borating agents (MeOB(OR)2) affords diverse symmetrical or unsymmetrical cis‐1,2‐diborylalkenes. The simple protocol for the diboration reaction can be extended to the iron‐catalyzed carboboration of alkynes with primary and, unprecedentedly, secondary alkyl halides, affording various tetrasubstituted monoborylalkenes in a highly stereoselective manner. DFT calculations indicate that a boryliron intermediate adds across the triple bond of an alkyne to afford an alkenyliron intermediate, which can react with the external trapping agents, borates and alkyl halides. In situ trapping experiments support the intermediacy of the alkenyl iron species using radical probe stubstrates. 相似文献
13.
Jingjie Yang Zhuofan Gui Yuli He Prof. Shaolin Zhu 《Angewandte Chemie (International ed. in English)》2023,62(28):e202304713
An attractive approach to selective functionalization of remote C−H bonds is a metal/hydride shift/cross-coupling reaction sequence. Complimentary to the heavily exploited 1,2-nickel/hydride shift along an sp3 chain, a chain-walking process, the 1,4-nickel/hydride shift along an sp2 chain is more complex. Here we report an unprecedented aryl-to-vinyl 1,4-nickel/hydride shift reaction, in which the migratory alkenylnickel species generated in situ is selectively trapped by one of various coupling partners, such as isocyanates, alkyl bromides, aryl chlorides or alkynyl bromides, allowing regio- and stereoselective access to trisubstituted alkenes. In contrast to the well-reported ipso-aryl coupling reactions, this strategy provides remote alkenyl C−H functionalized products with good yield and with excellent chemo-, regio- and E/Z-selectivity. 相似文献
14.
《Journal of organometallic chemistry》1987,319(2):C31-C34
A sterically bulky aryl or alkenyl group directly bonded to gold suppresses the rate of dissociation of the triphenylphosphine ligand from cis-alkenyl(or -aryl)dimethyl(triphenylphosphine)gold(III) leading to selective reductive elimination. 相似文献
15.
Tai CL Hung MS Pawar VD Tseng SL Song JS Hsieh WP Chiu HH Wu HC Hsieh MT Kuo CW Hsieh CC Tsao JP Chao YS Shia KS 《Organic & biomolecular chemistry》2008,6(3):447-450
A novel class of (5-(pent-1-enyl)thiophen-2-yl)pyrazole antagonists was discovered, many of which exhibited potent CB1 activity and good CB1/2 selectivity, suggesting that along with a 1,3-transposition of the carbonyl of the pyrazole 3-carboxamide, bioisosteric replacement of the conventional pyrazole 5-aryl group with a thienyl ring substituted with an appropriate alkenyl moiety is viable. 相似文献
16.
Shaozhong Wang 《Tetrahedron letters》2018,59(14):1317-1327
Propargylic carboxylates, as a type of easily available alkyne compounds, have attracted considerable attentions in recent decade. Under the catalysis of transition metal complex (Pd, Ru, Pt, Au, Rh etc), one of chemical transformations of propargylic carboxylate is 1,2-acyloxy migration. The resultant alkenyl metallocarbenoid or metal-containing species may undergo a variety of chemical transformations, leading to formation of carbocyclic and heterocyclic compounds. In this review, representative domino reactions initiated by 1,2-acyloxy migration of propargylic carboxylates are summarized, including pentannuations, cycloadditions and rearrangements. Some mechanistic discussions and synthetic applications are also included. 相似文献
17.
Prof. Dr. Dmitriy M. Volochnyuk Dr. Alina O. Gorlova Prof. Dr. Oleksandr O. Grygorenko 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(62):15277-15326
This review discusses recent advances in the chemistry of saturated boronic acids, boronates, and trifluoroborates. Applications of the title compounds in the design of boron-containing drugs are surveyed, with special emphasis on α-amino boronic derivatives. A general overview of saturated boronic compounds as modern tools to construct C(sp3)−C and C(sp3)-heteroatom bonds is given, including recent developments in the Suzuki-Miyaura and Chan-Lam cross-couplings, single-electron-transfer processes including metallo- and organocatalytic photoredox reactions, and transformations of boron “ate” complexes. Finally, an attempt to summarize the current state of the art in the synthesis of saturated boronic acids, boronates, and trifluoroborates is made, with a brief mention of the “classical” methods (transmetallation of organolithium/magnesium reagents with boron species, anti-Markovnikov hydroboration of alkenes, and the modification of alkenyl boron compounds) and a special focus on recent methodologies (boronation of alkyl (pseudo)halides, derivatives of carboxylic acids, alcohols, and primary amines, boronative C−H activation, novel approaches to alkene hydroboration, and 1,2-metallate-type rearrangements). 相似文献
18.
Hu TC Hsiao PI Wang TH Yang YW Chang CY Wu YH Sun WC Yu MS Lee CY Lo YH 《Dalton transactions (Cambridge, England : 2003)》2011,40(47):12663-12666
A new oxidation procedure of alkynes catalyzed by Tp(PPh(3))(CH(3)CN)Ru-Cl is presented, which provides an efficient way to obtain alkenyl 1,2-diketones via ruthenium alkenyl 1,2-diketone intermediates. In contrast, the analogous reactions with Tp(PPh(3))(PhCN)Ru-Cl gave rise to the ruthenium metallacycle complexes. 相似文献
19.
Gana Sanil Dr. Maciej Krzeszewski Dr. Wojciech Chaładaj Prof. Witold Danikiewicz Iryna Knysh Dr. Łukasz Dobrzycki Dr. Olga Staszewska-Krajewska Prof. Michał K. Cyrański Prof. Denis Jacquemin Prof. Daniel T. Gryko 《Angewandte Chemie (International ed. in English)》2023,62(49):e202311123
The tandem intramolecular hydroarylation of alkynes accompanied by a 1,2-aryl shift is described. Harnessing the unique electron-rich character of 1,4-dihydropyrrolo[3,2-b]pyrrole scaffold, we demonstrate that the hydroarylation of alkynes proceeds at the already occupied positions 2 and 5 leading to a 1,2-aryl shift. Remarkably, the reaction proceeds only in the presence of cationic gold catalyst, and it leads to heretofore unknown π-expanded, centrosymmetric pyrrolo[3,2-b]pyrroles. The utility is verified in the preparation of 13 products that bear six conjugated rings. The observed compatibility with various functional groups allows for increased tunability with regard to the photophysical properties as well as providing sites for further functionalization. Computational studies of the reaction mechanism revealed that the formation of the six-membered rings accompanied with a 1,2-aryl shift is both kinetically and thermodynamically favourable over plausible formation of products containing 7-membered rings. Steady-state UV/Visible spectroscopy reveals that upon photoexcitation, the prepared S-shaped N-doped nanographenes undergo mostly radiative relaxation leading to large fluorescence quantum yields. Their optical properties are rationalized through time-dependent density functional theory calculations. We anticipate that this chemistry will empower the creation of new materials with various functionalities. 相似文献
20.
Juba Ghouilem Morgane de Robichon Dr. Franck Le Bideau Dr. Angélique Ferry Dr. Samir Messaoudi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(2):491-511
Transition-metal-catalyzed C−H functionalization and photoredox nickel dual catalysis have emerged as innovative and powerful avenues for the synthesis of C-branched glycosides. These two concepts have been recently established and provide efficient and mild methods for accessing a series of valuable complex C-branched glycosides of great interest. Herein, recent developments in the synthesis of C-branched aryl/alkenyl/alkyl glycosides through these two approaches are highlighted. 相似文献