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1.
Vu T. Nguyen Viet D. Nguyen Graham C. Haug Ngan T. H. Vuong Hang T. Dang Hadi D. Arman Oleg V. Larionov 《Angewandte Chemie (International ed. in English)》2020,59(20):7921-7927
The development of efficient and selective C?N bond‐forming reactions from abundant feedstock chemicals remains a central theme in organic chemistry owing to the key roles of amines in synthesis, drug discovery, and materials science. Herein, we present a dual catalytic system for the N‐alkylation of diverse aromatic carbocyclic and heterocyclic amines directly with carboxylic acids, by‐passing their preactivation as redox‐active esters. The reaction, which is enabled by visible‐light‐driven, acridine‐catalyzed decarboxylation, provides access to N‐alkylated secondary and tertiary anilines and N‐heterocycles. Additional examples, including double alkylation, the installation of metabolically robust deuterated methyl groups, and tandem ring formation, further demonstrate the potential of the direct decarboxylative alkylation (DDA) reaction. 相似文献
2.
Visible‐Light‐Induced Decarboxylative Functionalization of Carboxylic Acids and Their Derivatives 下载免费PDF全文
Dr. Jun Xuan Prof. Dr. Zhao‐Guo Zhang Prof. Dr. Wen‐Jing Xiao 《Angewandte Chemie (International ed. in English)》2015,54(52):15632-15641
Visible‐light‐induced radical decarboxylative functionalization of carboxylic acids and their derivatives has recently received considerable attention as a novel and efficient method to create C? C and C? X bonds. Generally, this visible‐light‐promoted decarboxylation process can smoothly occur under mild reaction conditions with a broad range of substrates and an excellent functional‐group tolerance. The radical species formed from the decarboxylation step can participate in not only single photocatalytic transformations, but also dual‐catalytic cross‐coupling reactions by combining photoredox catalysis with other catalytic processes. Recent advances in this research area are discussed herein. 相似文献
3.
Visible Light‐Promoted Decarboxylative Di‐ and Trifluoromethylthiolation of Alkyl Carboxylic Acids 下载免费PDF全文
Dr. Lisa Candish Lena Pitzer Dr. Adrián Gómez‐Suárez Prof. Dr. Frank Glorius 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(14):4753-4756
Described herein is a new and straightforward decarboxylative di‐ and trifluoromethylthiolation of alkyl carboxylic acids promoted by visible light. This approach enables the synthesis of biologically relevant alkyl SCF2H and SCF3 compounds from cheap and abundant carboxylic acids. The method is operationally simple, using irradiation from household light sources, and its mild reaction conditions make it tolerant of a range of functional groups. The strategy employs electrophilic phthalimide‐derived di‐ and trifluoromethylthiolation reagents and exploits the ability of the imidyl radical to carry a radical chain. 相似文献
4.
Room‐Temperature Decarboxylative Alkynylation of Carboxylic Acids Using Photoredox Catalysis and EBX Reagents 下载免费PDF全文
Franck Le Vaillant Dr. Thibaut Courant Prof. Dr. Jerome Waser 《Angewandte Chemie (International ed. in English)》2015,54(38):11200-11204
Alkynes are used as building blocks in synthetic and medicinal chemistry, chemical biology, and materials science. Therefore, efficient methods for their synthesis are the subject of intensive research. Herein, we report the direct synthesis of alkynes from readily available carboxylic acids at room temperature under visible‐light irradiation. The combination of an iridium photocatalyst with ethynylbenziodoxolone (EBX) reagents allowed the decarboxylative alkynylation of carboxylic acids in good yields under mild conditions. The method could be applied to silyl‐, aryl‐, and alkyl‐ substituted alkynes. It was particularly successful in the case of α‐amino and α‐oxo acids derived from biomass. 相似文献
5.
《中国化学快报》2021,32(9):2777-2781
Silver-catalyzed decarboxylative C–H alkylation of cyclic aldimines with abundant aliphatic carboxylic acids has been realized under mild reaction conditions generating the corresponding products in moderate to good yields (32%–91%). In addition, a gram-scale reaction, late-stage modification of drug, synthetic transformation of the product, and further application of the catalytic strategy were also performed. Preliminary studies indicate that the reaction undergoes a radical process. 相似文献
6.
Giulia Bergonzini Carlo Cassani Carl‐Johan Wallentin 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(47):14272-14275
Simple and abundant carboxylic acids have been used as acyl radical precursor by means of visible‐light photoredox catalysis. By the transient generation of a reactive anhydride intermediate, this redox‐neutral approach offers a mild and rapid entry to high‐value heterocyclic compounds without the need of UV irradiation, high temperature, high CO pressure, tin reagents, or peroxides. 相似文献
7.
Dual Hypervalent Iodine(III) Reagents and Photoredox Catalysis Enable Decarboxylative Ynonylation under Mild Conditions 下载免费PDF全文
Hanchu Huang Guojin Zhang Prof. Dr. Yiyun Chen 《Angewandte Chemie (International ed. in English)》2015,54(27):7872-7876
A combination of hypervalent iodine(III) reagents (HIR) and photoredox catalysis with visible light has enabled chemoselective decarboxylative ynonylation to construct ynones, ynamides, and ynoates. This ynonylation occurs effectively under mild reaction conditions at room temperature and on substrates with various sensitive and reactive functional groups. The reaction represents the first HIR/photoredox dual catalysis to form acyl radicals from α‐ketoacids, followed by an unprecedented acyl radical addition to HIR‐bound alkynes. Its efficient construction of an mGlu5 receptor inhibitor under neutral aqueous conditions suggests future visible‐light‐induced biological applications. 相似文献
8.
Catalytic Access to Alkyl Bromides,Chlorides and Iodides via Visible Light‐Promoted Decarboxylative Halogenation 下载免费PDF全文
Dr. Adrián Gómez‐Suárez Satobhisha Mukherjee Prof. Dr. Frank Glorius 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(29):9971-9974
Herein is reported the catalytic, visible light‐promoted, decarboxylative halogenation (bromination, chlorination, and iodination) of aliphatic carboxylic acids. This operationally‐simple reaction tolerates a range of functional groups, proceeds at room temperature, and is redox neutral. By employing an iridium photocatalyst in concert with a halogen atom source, the use of stoichiometric metals such as silver, mercury, thallium, and lead can be circumvented. This reaction grants access to valuable synthetic building blocks from the large pool of cheap, readily available carboxylic acids. 相似文献
9.
Hypervalent Iodine Reagents Enable Chemoselective Deboronative/Decarboxylative Alkenylation by Photoredox Catalysis 下载免费PDF全文
Hanchu Huang Kunfang Jia Prof. Dr. Yiyun Chen 《Angewandte Chemie (International ed. in English)》2015,54(6):1881-1884
Chemoselective C(sp3)? C(sp2) coupling reactions under mild reaction conditions are useful for synthesizing alkyl‐substituted alkenes having sensitive functional groups. Reported here is a visible‐light‐induced chemoselective alkenylation through a deboronation/decarboxylation sequence under neutral aqueous reaction conditions at room temperature. This reaction represents the first hypervalent‐iodine‐enabled radical decarboxylative alkenylation reaction, and a novel benziodoxole‐vinyl carboxylic acid reaction intermediate was isolated. This C(sp3)? C(sp2) coupling reaction leads to aryl‐and acyl‐substituted alkenes containing various sensitive functional groups. The excellent chemoselectivity, stable reactants, and neutral aqueous reaction conditions of the reaction suggest future biomolecule applications. 相似文献
10.
Decarboxylative Conjunctive Cross‐coupling of Vinyl Boronic Esters using Metallaphotoredox Catalysis
Riccardo S. Mega Vincent K. Duong Adam Noble Varinder K. Aggarwal 《Angewandte Chemie (International ed. in English)》2020,59(11):4375-4379
The synthesis of complex alkyl boronic esters through conjunctive cross‐coupling of vinyl boronic esters with carboxylic acids and aryl iodides is described. The reaction proceeds under mild metallaphotoredox conditions and involves an unprecedented decarboxylative radical addition/cross‐coupling cascade of vinyl boronic esters. Excellent functional‐group tolerance is displayed, and application of a range of carboxylic acids, including secondary α‐amino acids, and aryl iodides provides efficient access to highly functionalized alkyl boronic esters. The decarboxylative conjunctive cross‐coupling was also applied to the synthesis of sedum alkaloids. 相似文献
11.
Quan‐Quan Zhou Wei Guo Wei Ding Xiong Wu Xi Chen Liang‐Qiu Lu Wen‐Jing Xiao 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(38):11348-11351
Visible‐light‐induced photocatalytic decarboxylative alkynylations of carboxylic acids have been developed for the first time. The reaction features extremely mild conditions, broad substrate scope, and avoids additional oxidants. Importantly, a decarboxylative carbonylative alkynylation has also been carried out in the presence of carbon monoxide (CO) under photocatalytic conditions, which affords valuable ynones in high yields at room temperature. 相似文献
12.
Merging Photoredox and Nickel Catalysis: The Direct Synthesis of Ketones by the Decarboxylative Arylation of α‐Oxo Acids 下载免费PDF全文
Dr. Lingling Chu Jeffrey M. Lipshultz Prof. Dr. David W. C. MacMillan 《Angewandte Chemie (International ed. in English)》2015,54(27):7929-7933
The direct decarboxylative arylation of α‐oxo acids has been achieved by synergistic visible‐light‐mediated photoredox and nickel catalysis. This method offers rapid entry to aryl and alkyl ketone architectures from simple α‐oxo acid precursors via an acyl radical intermediate. Significant substrate scope is observed with respect to both the oxo acid and arene coupling partners. This mild decarboxylative arylation can also be utilized to efficiently access medicinal agents, as demonstrated by the rapid synthesis of fenofibrate. 相似文献
13.
Herein, unprecedented rhenium‐catalyzed decarboxylative oxytri‐/difluoromethylation and Heck‐type trifluoromethylation of styrenes have been developed by using hypervalent iodine(III) reagents derived from cheap, stable, and easy‐handling fluorinated carboxylic acids. Mechanistic studies revealed a radical decarboxylative trifluoromethylation pathway occurring in these reactions. 相似文献
14.
Visible‐Light‐Mediated Decarboxylative Radical Additions to Vinyl Boronic Esters: Rapid Access to γ‐Amino Boronic Esters 下载免费PDF全文
Dr. Adam Noble Riccardo S. Mega Dr. Daniel Pflästerer Dr. Eddie L. Myers Prof. Dr. Varinder K. Aggarwal 《Angewandte Chemie (International ed. in English)》2018,57(8):2155-2159
The synthesis of alkyl boronic esters by direct decarboxylative radical addition of carboxylic acids to vinyl boronic esters is described. The reaction proceeds under mild photoredox catalysis and involves an unprecedented single‐electron reduction of an α‐boryl radical intermediate to the corresponding anion. The reaction is amenable to a diverse range of substrates, including α‐amino, α‐oxy, and alkyl carboxylic acids, thus providing a novel method to rapidly access boron‐containing molecules of potential biological importance. 相似文献
15.
Xiao‐Li Lai Xiao‐Min Shu Jinshuai Song Hai‐Chao Xu 《Angewandte Chemie (International ed. in English)》2020,59(26):10626-10632
Decarboxylative C?H functionalization reactions are highly attractive methods for forging carbon–carbon bonds considering their inherent step‐ and atom‐economical features and the pervasiveness of carboxylic acids and C?H bonds. An ideal approach to achieve these dehydrogenative transformations is through hydrogen evolution without using any chemical oxidants. However, effective couplings by decarboxylative carbon–carbon bond formation with proton reduction remain an unsolved challenge. Herein, we report an electrophotocatalytic approach that merges organic electrochemistry with photocatalysis to achieve the efficient direct decarboxylative C?H alkylation and carbamoylation of heteroaromatic compounds through hydrogen evolution. This electrophotocatalytic method, which combines the high efficiency and selectivity of photocatalysis in promoting decarboxylation with the superiority of electrochemistry in effecting proton reduction, enables the efficient coupling of a wide range of heteroaromatic bases with a variety of carboxylic acids and oxamic acids. Advantageously, this method is scalable to decagram amounts, and applicable to the late‐stage functionalization of drug molecules. 相似文献
16.
Silver‐Catalyzed Decarboxylative Trifluoromethylthiolation of Aliphatic Carboxylic Acids in Aqueous Emulsion 下载免费PDF全文
Dr. Feng Hu Xinxin Shao Dianhu Zhu Prof. Dr. Long Lu Prof. Dr. Qilong Shen 《Angewandte Chemie (International ed. in English)》2014,53(24):6105-6109
A silver‐catalyzed decarboxylative trifluoromethylthiolation of secondary and tertiary carboxylic acids under mild conditions tolerates a wide range of functional groups. The reaction was dramatically accelerated by its performance in an aqueous emulsion, which was formed by the addition of sodium dodecyl sulfate to water. It was proposed that the radical, which was generated from the silver‐catalyzed decarboxylation in the “oil‐in‐water” droplets, could easily react with the trifluoromethylthiolating reagent to form the product. 相似文献
17.
Soumitra Agasti Tapas Pal Tapas Kumar Achar Siddhartha Maiti Debasis Pal Smita Mandal Kishan Daud Goutam Kumar Lahiri Debabrata Maiti 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(32):11155-11159
α,β‐Alkenyl carboxylic acids undergo CuII‐mediated decarboxylative annulation reactions with aliphatic cyclic ketones to provide synthetically valuable di‐heterocycles. The annulation process tolerates a variety of aliphatic ketones and heterocyclic alkenyl carboxylic acids, producing substituted fused furan derivatives with complete regioselectivity. The current protocol offers a synthetically applicable pathway to construct a variety of oligo‐heterocycles through Cu‐mediated single‐electron transfer and decarboxylation. Notably, synthesis of relatively inaccessible di‐heterocycles has been achieved successfully using this protocol. 相似文献
18.
Vu T. Nguyen Viet D. Nguyen Graham C. Haug Ngan T. H. Vuong Hang T. Dang Dr. Hadi D. Arman Dr. Oleg V. Larionov 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(20):7995-8001
The development of efficient and selective C−N bond-forming reactions from abundant feedstock chemicals remains a central theme in organic chemistry owing to the key roles of amines in synthesis, drug discovery, and materials science. Herein, we present a dual catalytic system for the N-alkylation of diverse aromatic carbocyclic and heterocyclic amines directly with carboxylic acids, by-passing their preactivation as redox-active esters. The reaction, which is enabled by visible-light-driven, acridine-catalyzed decarboxylation, provides access to N-alkylated secondary and tertiary anilines and N-heterocycles. Additional examples, including double alkylation, the installation of metabolically robust deuterated methyl groups, and tandem ring formation, further demonstrate the potential of the direct decarboxylative alkylation (DDA) reaction. 相似文献
19.
Palladium‐Catalyzed Atom‐Transfer Radical Cyclization at Remote Unactivated C(sp3)−H Sites: Hydrogen‐Atom Transfer of Hybrid Vinyl Palladium Radical Intermediates 下载免费PDF全文
Maxim Ratushnyy Marvin Parasram Yang Wang Prof. Dr. Vladimir Gevorgyan 《Angewandte Chemie (International ed. in English)》2018,57(10):2712-2715
A novel mild, visible‐light‐induced palladium‐catalyzed hydrogen atom translocation/atom‐transfer radical cyclization (HAT/ATRC) cascade has been developed. This protocol involves a 1,5‐HAT process of previously unknown hybrid vinyl palladium radical intermediates, thus leading to iodomethyl carbo‐ and heterocyclic structures. 相似文献
20.
The exceptional versatility of carboxylic acids has been extensively exploited in organic synthesis across several decades. There has been a recent upsurge of radical decarboxylative transformations. The process can be initiated under mild conditions, and the resultant radicals have orthogonal reactivities to closed-shell species, thus providing immense opportunities for streamlining novel reactions. The use of free carboxylic acids is the most desirable owing to its high atom and step economy. Aiming to demonstrate the attractiveness of the strategy and to inspire chemists to tackle existing challenges, this review outlines the recent advances on radical decarboxylative functionalization of free carboxylic acids. 相似文献