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1.
Photochemical Carbopyridylation of Alkenes Using N-Alkenoxypyridinium Salts as Bifunctional Reagents
Gangadhar Rao Mathi Yujin Jeong Yonghoon Moon Prof. Dr. Sungwoo Hong 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(5):2065-2070
N-Alkenoxypyridinium salts have been used as synthons for the umpolung reaction of enolates for the preparation of α-functionalized carbonyl compounds. In contrast, we found that the photoreduction of N-alkenoxypyridinium salts generates α-carbonyl radicals after cleavage of the N−O bond, thereby allowing simultaneous incorporation of α-keto and pyridyl groups across unactivated alkenes. In the process, the formed α-carbonyl radicals engage unactivated alkenes to afford alkyl radical intermediates poised for subsequent addition to pyridinium salts, which ultimately affords a variety of γ-pyridyl ketones under mild reaction conditions. This transformation is characterized by a broad substrate scope and good functional-group compatibility, and the utility of this transformation was further demonstrated by the late-stage functionalization of complex biorelevant molecules. 相似文献
2.
Jinwon Jeon Yu‐Tao He Sanghoon Shin Sungwoo Hong 《Angewandte Chemie (International ed. in English)》2020,59(1):281-285
The photocatalyzed ortho‐selective migration on a pyridyl ring has been achieved for the site‐selective trifluoromethylative pyridylation of unactivated alkenes. The overall process is initiated by the selective addition of a CF3 radical to the alkene to provide a nucleophilic alkyl radical intermediate, which enables an intramolecular endo addition exclusively to the ortho‐position of the pyridinium salt. Both secondary and tertiary alkyl radicals are well‐suited for addition to the C2‐position of pyridinium salts to ultimately provide synthetically valuable C2‐fluoroalkyl functionalized pyridines. Moreover, the method was successfully applied to the reaction with P‐centered radicals. The utility of this transformation was further demonstrated by the late‐stage functionalization of complex bioactive molecules. 相似文献
3.
Heng Jiang Gesa Seidler Armido Studer 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(46):16680-16684
Two‐component Giese type radical additions are highly practical and established reactions. Herein, three‐component radical conjugate additions of unactivated alkenes to Michael acceptors are reported. Amidyl radicals, oxidatively generated from α‐amido oxy acids using redox catalysis, act as the third reaction component which add to the unactivated alkenes. The adduct radicals engage in Giese type additions to Michael acceptors to provide, after reduction, the three‐component products in an overall alkene carboamination reaction. Transformations which can be conducted under practical mild conditions feature high functional group tolerance and broad substrate scope. 相似文献
4.
Jinwon Jeon Dr. Yu-Tao He Sanghoon Shin Prof. Dr. Sungwoo Hong 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(1):287-291
The photocatalyzed ortho-selective migration on a pyridyl ring has been achieved for the site-selective trifluoromethylative pyridylation of unactivated alkenes. The overall process is initiated by the selective addition of a CF3 radical to the alkene to provide a nucleophilic alkyl radical intermediate, which enables an intramolecular endo addition exclusively to the ortho-position of the pyridinium salt. Both secondary and tertiary alkyl radicals are well-suited for addition to the C2-position of pyridinium salts to ultimately provide synthetically valuable C2-fluoroalkyl functionalized pyridines. Moreover, the method was successfully applied to the reaction with P-centered radicals. The utility of this transformation was further demonstrated by the late-stage functionalization of complex bioactive molecules. 相似文献
5.
Kangjae Lee Seojin Lee Namhoon Kim Seonyul Kim Sungwoo Hong 《Angewandte Chemie (International ed. in English)》2020,59(32):13379-13384
A general strategy for visible‐light‐enabled site‐selective trifluoromethylative pyridylation of unactivated alkenes has been developed using pyridines and triflic anhydride (Tf2O). Intriguingly, the N‐triflylpyridinium salts, generated in situ from pyridines and Tf2O, serve as effective modular bifunctional reagents to install both CF3 and pyridyl groups to various olefins while controlling C4‐selectivity in radical addition to the pyridine core. This synthetic route exhibited broad substrate scope under metal‐free and mild photocatalytic conditions, granting efficient access to valuable C4‐alkylated pyridines and quinolines without requiring prefunctionalization of the reaction site. 相似文献
6.
Daniel Kaiser Prof. Luís F. Veiros Prof. Dr. Nuno Maulide 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(14):4727-4732
The Brønsted acid‐mediated reaction of unactivated alkynes with aryl sulfoxides leads to simultaneous hydration and intermolecular C?C bond formation. This solvent‐ and metal‐free transformation directly delivers α‐arylated carbonyl compounds as the products of a formal hydrative arylation in an atom‐economical manner. The products bear useful synthetic handles for further functionalization. 相似文献
7.
Wang Wang Chao Ding Yangyang Li Zheqi Li Yuqiang Li Long Peng Guoyin Yin 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(14):4660-4664
An unprecedented arylboration of unactivated terminal alkenes, featuring 1,n‐regioselectivity, has been achieved by nickel catalysis. The nitrogen‐based ligand plays an essential role in the success of this three‐component reaction. This transformation displays good regioselectivity and excellent functional‐group tolerance. In addition, the incorporation of a boron group into the products provides substantial opportunities for further transformations. Also demonstrated is that the products can be readily transformed into pharmaceutically relevant molecules. Unexpectedly, preliminary mechanistic studies indicate that although the metal migration favors the α‐position of boron, selective and decisive bond formation is favored at the benzylic position. 相似文献
8.
Amidyl Radicals by Oxidation of α‐Amido‐oxy Acids: Transition‐Metal‐Free Amidofluorination of Unactivated Alkenes
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Heng Jiang Prof. Dr. Armido Studer 《Angewandte Chemie (International ed. in English)》2018,57(33):10707-10711
A three‐component transition‐metal‐free amidofluorination of unactivated alkenes and styrenes is presented. α‐Amido‐oxy acids are introduced as efficient and easily accessible amidyl radical precursors that are oxidized by a photoexcited organic sensitizer (Mes‐Acr‐Me) to the corresponding carboxyl radical. Sequential CO2 and aldehyde/ketone fragmentation leads to an N‐centered radical that adds to an alkene. Commercial Selectfluor is used to trap the adduct radical through fluorine‐atom transfer. The transformation features by high functional‐group tolerance, broad substrate scope, and practical mild conditions. Mechanistic studies support the radical nature of the cascade. 相似文献
9.
Trifluoromethylation‐Initiated Remote Cross‐Coupling of Carbonyl Compounds to Form Carbon–Heteroatom/Carbon Bonds
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Lin Huang Dr. Sheng‐Cai Zheng Prof. Dr. Bin Tan Prof. Dr. Xin‐Yuan Liu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(18):6718-6722
By involving the reversal of conventional reactivity expectations without external oxidants, we describe a novel and convenient protocol of remote cross‐coupling of carbonyl compounds with a series of common and simple nucleophiles. This cross‐coupling is triggered by radical trifluoromethylation of alkenes, thereby achieving highly selective remote difunctionalization of alkenes and α‐position of the carbonyl group for facile access to trifluoromethyl α‐halo‐ and α‐cyanocarbonyl compounds. The reaction exhibits a broad substrate scope with excellent functionality tolerance and many different types of nucleophiles; further synthetic applicability of the obtained compounds proved to be suitable, thus showing great potential for synthetic utility. 相似文献
10.
Copper‐Catalyzed Intermolecular Carboetherification of Unactivated Alkenes by Alkyl Nitriles and Alcohols
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Claire Chatalova‐Sazepin Dr. Qian Wang Prof. Dr. Glenn M. Sammis Prof. Dr. Jieping Zhu 《Angewandte Chemie (International ed. in English)》2015,54(18):5443-5446
A three‐component carboetherification of unactivated alkenes has been developed allowing the rapid building of complexity from simple starting materials. A wide range of α‐substituted styrenes underwent smooth reactions with unactivated alkyl nitriles and alcohols to afford γ‐alkoxy alkyl nitriles with concomitant generation of a quaternary carbon center. A radical clock experiment provided clear‐cut evidence that the reaction proceeds through a tertiary alkyl radical intermediate. 相似文献
11.
Yangyang Li Hailiang Pang Dong Wu Zheqi Li Wang Wang Hong Wei Ying Fu Guoyin Yin 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(26):8964-8968
An unprecedented nickel‐catalyzed 1,1‐alkylboration of electronically unbiased alkenes has been developed, providing straightforward access to secondary aliphatic boronic esters from readily available materials under very mild reaction conditions. The regioselectivity of this reaction is governed by a unique pyridyl carboxamide ligated catalyst, rather than the substrates. Moreover, this transformation shows excellent chemo‐ and regio‐selectivity and remarkably good functional‐group tolerance. We also demonstrate that under balloon pressure, ethylene can also be utilized as a substrate. Additionally, competence experiments indicate that selective bond formation is favored at the α‐position of boron and preliminary mechanistic studies indicate that the key step in this three‐component reaction involves a 1,2‐nickel migration. 相似文献
12.
Xiu‐Long Yang Jia‐Dong Guo Hongyan Xiao Ke Feng Bin Chen Chen‐Ho Tung Li‐Zhu Wu 《Angewandte Chemie (International ed. in English)》2020,59(13):5365-5370
Radical formation is the initial step for conventional radical chemistry. Reported herein is a unified strategy to generate radicals in situ from aromatic β‐ketoesters by using a photocatalyst. Under visible‐light irradiation, a small amount of photocatalyst fac‐Ir(ppy)3 generates a transient α‐carbonyl radical and persistent ketyl radical in situ. In contrast to the well‐established approaches, neither stoichiometric external oxidant nor reductant is required for this reaction. The synthetic utility is demonstrated by pinacol coupling of ketyl radicals and benzannulation of α‐carbonyl radicals with alkynes to give a series of highly substituted 1‐naphthols in good to excellent yields. The readily available photocatalyst, mild reaction conditions, broad substrate scope, and high functional‐group tolerance make this reaction a useful synthetic tool. 相似文献
13.
Palladium‐Catalyzed Oxidative Difunctionalization of Alkenes with α‐Carbonyl Alkyl Bromides Initiated through a Heck‐type Insertion: A Route to Indolin‐2‐ones
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Jian‐Hong Fan Wen‐Ting Wei Ming‐Bo Zhou Dr. Ren‐Jie Song Prof. Dr. Jin‐Heng Li 《Angewandte Chemie (International ed. in English)》2014,53(26):6650-6654
The oxidative interception of various σ‐alkyl palladium(II) intermediates with additional reagents for the difunctionalization of alkenes is an important research area. A new palladium‐catalyzed oxidative difunctionalization reaction of alkenes with α‐carbonyl alkyl bromides is described, in which the σ‐alkyl palladium(II) intermediate is generated through a Heck insertion and trapped using an aryl C(sp2)? H bond. This method can be applied to various α‐carbonyl alkyl bromides, including primary, secondary, and tertiary α‐bromoalkyl esters, ketones, and amides. 相似文献
14.
Copper‐Catalyzed Enantioselective Markovnikov Protoboration of α‐Olefins Enabled by a Buttressed N‐Heterocyclic Carbene Ligand
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Yuan Cai Xin‐Tuo Yang Dr. Shuo‐Qing Zhang Feng Li Yu‐Qing Li Lin‐Xin Ruan Prof. Dr. Xin Hong Prof. Dr. Shi‐Liang Shi 《Angewandte Chemie (International ed. in English)》2018,57(5):1376-1380
Reported is a highly enantioselective copper‐catalyzed Markovnikov protoboration of unactivated terminal alkenes. A variety of simple and abundant feedstock α‐olefins bearing a diverse array of functional groups and heterocyclic substituents can be used as substrates, and the reaction proceeds under mild reaction conditions at ambient temperature to provide expedient access to enantioenriched alkylboronic esters in good regioselectivity and with excellent enantiocontrol. Critical to the success of the protocol was the development and application of a novel, sterically hindered N‐heterocyclic carbene, (R,R,R,R)‐ANIPE, as the ligand for copper. 相似文献
15.
Platinum(II) Olefin Hydroarylation Catalysts: Tuning Selectivity for the anti‐Markovnikov Product
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Marie L. Clement Kyle A. Grice Avery T. Luedtke Werner Kaminsky Prof. Karen I. Goldberg 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(52):17287-17291
PtII complexes containing unsymmetrical (pyridyl)pyrrolide ligands are shown to catalyze the hydroarylation of unactivated alkenes with selectivity for the anti‐Markovnikov product. Substitution on the pyrrolide portion of the ligand allows effective tuning of the selectivity to anti‐Markovnikov alkylarene products, whereas substitution on the pyridyl portion can promote competitive alkenylarene production. 相似文献
16.
Lu Wang Minxu Shi Xiaoping Chen Nicholas Su Weili Luo Xiaheng Zhang 《Angewandte Chemie (International ed. in English)》2023,62(52):e202314312
Nitrogen-centered radicals (NCRs) have been widely recognized as versatile synthetic intermediates for the construction of nitrogen containing molecules of high value. As such, there has been a long-standing interest in the field of organic synthesis to develop novel nitrogen-based radicals and explore their inherent reactivity. In this study, we present the generation of aromatic N-heterocyclic radicals and their application in a novel and diverse functionalization of unactivated alkenes. Bench-stable aromatic N-heterocyclic pyridinium salts were employed as crucial NCR precursors, which enabled the efficient conversion of various unactivated alkenes into medicinally relevant alkylated N-heterocyclic amines. This approach offers an unexplored retrosynthetic disconnection for the synthesis of related molecules that commonly possess therapeutic value. Furthermore, this platform can be extended to the synthesis of densely functionalized heterocyclic amines by utilizing disulfides and diethyl bromomalonate as radical quenchers. Mechanistic investigations indicate an energy transfer (EnT) pathway involving the formation of a transient aromatic N-heterocyclic radical, radical addition to unactivated alkenes, and subsequent generation of the amination product through either hydrogen atom transfer (HAT) or radical addition processes. 相似文献
17.
Peng Xiong Fan Xu Xiang‐Yang Qian Yared Yohannes Dr. Jinshuai Song Prof. Dr. Xin Lu Prof. Dr. Hai‐Chao Xu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(13):4379-4383
A copper‐catalyzed oxidative amination of unactivated internal alkenes has been developed. The Wacker‐type oxidative alkene amination reaction is traditionally catalyzed by a palladium through a mechanism involving aminopalladation and β‐hydride elimination. Replacing the precious and scarce palladium with a cheap and abundant copper for this transformation has been challenging because of the difficulty associated with the aminocupration of internal alkenes. The combination of a simple copper salt, without additional ligand, as the catalyst and Dess–Martin periodinane as the oxidant, promotes efficiently the oxidative amination of allylic carbamates and ureas bearing di‐ and trisubstituted alkenes leading to oxazolidinones and imidazolidinones. Preliminary mechanistic studies suggested a hybrid radical–organometallic mechanism involving an amidyl radical cyclization to form the key C?N bond. 相似文献
18.
Songlin Zheng Zimin Chen Yuanyuan Hu Xiaoxiang Xi Zixuan Liao Weirong Li Weiming Yuan 《Angewandte Chemie (International ed. in English)》2020,59(41):17910-17916
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
19.
Alkenylation of C(sp3)−H Bonds by Zincation/Copper‐Catalyzed Cross‐Coupling with Iodonium Salts
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Dr. Chuan Liu Prof. Dr. Qiu Wang 《Angewandte Chemie (International ed. in English)》2018,57(17):4727-4731
α‐Vinylation of phosphonates, phosphine oxides, sulfones, sulfonamides, and sulfoxides has been achieved by selective C?H zincation and copper‐catalyzed C(sp3)?C(sp2) cross‐coupling reaction using vinylphenyliodonium salts. The vinylation transformation proceeds in high efficiency and stereospecificity under mild reaction conditions. This zincative cross‐coupling reaction represents a general alkenylation strategy, which is also applicable for α‐alkenylation of esters, amides, and nitriles in the synthesis of β,γ‐unsaturated carbonyl compounds. 相似文献
20.
Kangjae Lee Seojin Lee Namhoon Kim Seonyul Kim Prof. Dr. Sungwoo Hong 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(32):13481-13486
A general strategy for visible-light-enabled site-selective trifluoromethylative pyridylation of unactivated alkenes has been developed using pyridines and triflic anhydride (Tf2O). Intriguingly, the N-triflylpyridinium salts, generated in situ from pyridines and Tf2O, serve as effective modular bifunctional reagents to install both CF3 and pyridyl groups to various olefins while controlling C4-selectivity in radical addition to the pyridine core. This synthetic route exhibited broad substrate scope under metal-free and mild photocatalytic conditions, granting efficient access to valuable C4-alkylated pyridines and quinolines without requiring prefunctionalization of the reaction site. 相似文献