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1.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(41):12793-12797
The alkoxyl radical is an essential and prevalent reactive intermediate for chemical and biological studies. Here we report the first donor–acceptor complex‐enabled alkoxyl radical generation under metal‐free reaction conditions induced by visible light. Hantzsch ester forms the key donor–acceptor complex with N ‐alkoxyl derivatives, which is elucidated by a series of spectrometry and mechanistic experiments. Selective C(sp3)‐C(sp3) bond cleavage and allylation/alkenylation is demonstrated for the first time using this photocatalyst‐free approach with linear primary, secondary, and tertiary alkoxyl radicals. 相似文献
2.
Tertiary‐Alcohol‐Directed Functionalization of Remote C(sp3)−H Bonds by Sequential Hydrogen Atom and Heteroaryl Migrations
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Xinxin Wu Mingyang Wang Leitao Huan Dongping Wang Jinwei Wang Prof. Dr. Chen Zhu 《Angewandte Chemie (International ed. in English)》2018,57(6):1640-1644
Reported for the first time is a tertiary‐alcohol‐guided heteroarylation of remote C(sp3)?H bonds. The mild and direct generation of alkoxyl radicals from alcohols is enabled by visible‐light photocatalysis. A remote hydrogen atom and heteroaryl migration sequence are involved in the reaction. Many sensitive groups remain intact in the reaction, thus illustrating wide functional‐group compatibility. This protocol provides a practical strategy for the late‐stage modification of alkyl ketones. 相似文献
3.
Prof. Dr. Daniel Solé Francesco Mariani Prof. Dr. M.‐Lluïsa Bennasar Dr. Israel Fernández 《Angewandte Chemie (International ed. in English)》2016,55(22):6467-6470
A palladium‐catalyzed carbene insertion into C(sp3)?H bonds leading to pyrrolidines was developed. The coupling reaction can be catalyzed by both Pd0 and PdII, is regioselective, and shows a broad functional group tolerance. This reaction is the first example of palladium‐catalyzed C(sp3)?C(sp3) bond assembly starting from diazocarbonyl compounds. DFT calculations revealed that this direct C(sp3)?H bond functionalization reaction involves an unprecedented concerted metalation–deprotonation step. 相似文献
4.
《Angewandte Chemie (International ed. in English)》2017,56(9):2478-2481
Carbon–carbon bond cleavage/functionalization is synthetically valuable, and selective carbonyl−C(sp3) bond cleavage/alkynylation presents a new perspective in constructing ynamides, ynoates, and ynones. Reported here is the first alkoxyl‐radical‐enabled carbonyl−C(sp3) bond cleavage/alkynylation reaction by photoredox catalysis. The use of novel cyclic iodine(III) reagents are essential for β‐carbonyl alkoxyl radical generation from β‐carbonyl alcohols, including alcohols with high redox potential ( >2.2 V vs. SCE in MeCN). β‐Amide, β‐ester, and β‐ketone alcohols yield ynamides, ynoates, and ynones, respectively, for the first time, with excellent regio‐ and chemoselectivity under mild reaction conditions. 相似文献
5.
Shuo Wu Xinxin Wu Dongping Wang Chen Zhu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(5):1513-1517
Regioselective incorporation of a particular functional group into aliphatic sites by direct activation of unreactive C?H bonds is of great synthetic value. Despite advances in radical‐mediated functionalization of C(sp3)?H bonds by a hydrogen‐atom transfer process, the site‐selective vinylation of remote C(sp3)?H bonds still remains underexplored. Reported herein is a new protocol for the regioselective vinylation of unactivated C(sp3)?H bonds. The remote C(sp3)?H activation is promoted by a C‐centered radical instead of the commonly used N and O radicals. The reaction possesses high product diversity and synthetic efficiency, furnishing a plethora of synthetically valuable E alkenes bearing tri‐/di‐/mono‐fluoromethyl and perfluoroalkyl groups. 相似文献
6.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(9):2518-2521
Carbon–carbon bond cleavage/functionalization is synthetically valuable, and selective carbonyl−C(sp3) bond cleavage/alkynylation presents a new perspective in constructing ynamides, ynoates, and ynones. Reported here is the first alkoxyl‐radical‐enabled carbonyl−C(sp3) bond cleavage/alkynylation reaction by photoredox catalysis. The use of novel cyclic iodine(III) reagents are essential for β‐carbonyl alkoxyl radical generation from β‐carbonyl alcohols, including alcohols with high redox potential ( >2.2 V vs. SCE in MeCN). β‐Amide, β‐ester, and β‐ketone alcohols yield ynamides, ynoates, and ynones, respectively, for the first time, with excellent regio‐ and chemoselectivity under mild reaction conditions. 相似文献
7.
Ronan Rocaboy Ioannis Anastasiou Olivier Baudoin 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(41):14767-14770
The intramolecular coupling of two C(sp3)?H bonds to forge a C(sp3)?C(sp3) bond is enabled by 1,4‐Pd shift from a trisubstituted aryl bromide. Contrary to most C(sp3)?C(sp3) cross‐dehydrogenative couplings, this reaction operates under redox‐neutral conditions, with the C?Br bond acting as an internal oxidant. Furthermore, it allows the coupling between two moderately acidic primary or secondary C?H bonds, which are adjacent to an oxygen or nitrogen atom on one side, and benzylic or adjacent to a carbonyl group on the other side. A variety of valuable fused heterocycles were obtained from easily accessible ortho‐bromophenol and aniline precursors. The second C?H bond cleavage was successfully replaced with carbonyl insertion to generate other types of C(sp3)‐C(sp3) bonds. 相似文献
8.
He Wang Guodong Tang Xingwei Li 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(44):13241-13244
Nitrogenation by direct functionalization of C H bonds represents an important strategy for constructing C N bonds. Rhodium(III)‐catalyzed direct amidation of unactivated C(sp3) H bonds is rare, especially under mild reaction conditions. Herein, a broad scope of C(sp3) H bonds are amidated under rhodium catalysis in high efficiency using 3‐substituted 1,4,2‐dioxazol‐5‐ones as the amide source. The protocol broadens the scope of rhodium(III)‐catalyzed C(sp3) H activation chemistry, and is applicable to the late‐stage functionalization of natural products. 相似文献
9.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(7):1907-1910
A redox‐neutral, light‐mediated functionalization of unactivated C(sp3)−H bonds via iminyl radicals is presented here. A 1,5‐H transfer followed by the functionalization of a C(sp2)−H bond takes place in aqueous media producing a variety of elaborated fused ketones. Mechanistic investigations have revealed 1,5‐H transfer as the reversible, rate‐determining step in this transformation. Divergent scaffolds are also accessible via C(sp3)−N bond formation upon a careful choice of the reaction additives. 相似文献
10.
Dr. Candice L. Joe Prof. Abigail G. Doyle 《Angewandte Chemie (International ed. in English)》2016,55(12):4040-4043
Using nickel and photoredox catalysis, the direct functionalization of C(sp3)?H bonds of N‐aryl amines by acyl electrophiles is described. The method affords a diverse range of α‐amino ketones at room temperature and is amenable to late‐stage coupling of complex and biologically relevant groups. C(sp3)?H activation occurs by photoredox‐mediated oxidation to generate α‐amino radicals which are intercepted by nickel in catalytic C(sp3)?C coupling. The merger of these two modes of catalysis leverages nickel's unique properties in alkyl cross‐coupling while avoiding limitations commonly associated with transition‐metal‐mediated C(sp3)?H activation, including requirements for chelating directing groups and high reaction temperatures. 相似文献
11.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(43):13509-13513
The first oxidative C(sp3)−H/C(sp3)−H cross‐dehydrogenative coupling (CDC) reaction promoted by an internal oxidant is reported. This copper‐catalyzed CDC reaction of oxime acetates and trifluoromethyl ketones provides a simple and efficient approach towards 2‐trifluoromethyldihydropyrrol‐2‐ol derivatives in a highly diastereoselective manner by cascade C(sp3)−C(sp3) bond formation and cyclization. These products were further transformed into various significant and useful trifluoromethylated heterocyclic compounds, such as trifluoromethylated furan, thiophene, pyrrole, dihydropyridazine, and pyridazine derivatives. A trifluoromethylated analogue of an Aβ42 lowering agent was also synthesized smoothly. Preliminary mechanistic studies indicated that this reaction involves a copper(I)/copper(III) catalytic cycle with the oxime acetate acting as an internal oxidant. 相似文献
12.
He Wang Guodong Tang Xingwei Li 《Angewandte Chemie (International ed. in English)》2015,54(44):13049-13052
Nitrogenation by direct functionalization of C H bonds represents an important strategy for constructing C N bonds. Rhodium(III)‐catalyzed direct amidation of unactivated C(sp3) H bonds is rare, especially under mild reaction conditions. Herein, a broad scope of C(sp3) H bonds are amidated under rhodium catalysis in high efficiency using 3‐substituted 1,4,2‐dioxazol‐5‐ones as the amide source. The protocol broadens the scope of rhodium(III)‐catalyzed C(sp3) H activation chemistry, and is applicable to the late‐stage functionalization of natural products. 相似文献
13.
Site‐Selective δ‐C(sp3)−H Alkylation of Amino Acids and Peptides with Maleimides via a Six‐Membered Palladacycle
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Bei‐Bei Zhan Ya Li Jing‐Wen Xu Xing‐Liang Nie Dr. Jun Fan Liang Jin Prof. Dr. Bing‐Feng Shi 《Angewandte Chemie (International ed. in English)》2018,57(20):5858-5862
The site‐selective functionalization of unactivated C(sp3)?H bonds remains one of the greatest challenges in organic synthesis. Herein, we report on the site‐selective δ‐C(sp3)?H alkylation of amino acids and peptides with maleimides via a kinetically less favored six‐membered palladacycle in the presence of more accessible γ‐C(sp3)?H bonds. Experimental studies revealed that C?H bond cleavage occurs reversibly and preferentially at γ‐methyl over δ‐methyl C?H bonds while the subsequent alkylation proceeds exclusively at the six‐membered palladacycle that is generated by δ‐C?H activation. The selectivity can be explained by the Curtin–Hammett principle. The exceptional compatibility of this alkylation with various oligopeptides renders this procedure valuable for late‐stage peptide modifications. Notably, this process is also the first palladium(II)‐catalyzed Michael‐type alkylation reaction that proceeds through C(sp3)?H activation. 相似文献
14.
Palladium(0)/PAr3‐Catalyzed Intermolecular Amination of C(sp3)H Bonds: Synthesis of β‐Amino Acids
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Jian He Toshihiko Shigenari Prof. Dr. Jin‐Quan Yu 《Angewandte Chemie (International ed. in English)》2015,54(22):6545-6549
An intermolecular C(sp3)? H amination using a Pd0/PAr3 catalyst was developed. The reaction begins with oxidative addition of R2N? OBz to a Pd0/PAr3 catalyst and subsequent cleavage of a C(sp3)? H bond by the generated Pd? NR2 intermediate. The catalytic cycle proceeds without the need for external oxidants in a similar manner to the extensively studied palladium(0)‐catalyzed C? H arylation reactions. The electron‐deficient triarylphosphine ligand is crucial for this C(sp3)? H amination reaction to occur. 相似文献
15.
Eric Tan Margherita Zanini Antonio M. Echavarren 《Angewandte Chemie (International ed. in English)》2020,59(26):10470-10473
An Ir‐catalyzed C(sp3)?H alkynylation of aliphatic ketones, aldehydes, and alcohols was achieved by using the corresponding oxime derivatives and a IrIII catalyst. This general reaction is selective towards primary C(sp3)?H bonds and can be used for the late‐stage C?H alkynylation of complex molecules. 相似文献
16.
Jian He Toshihiko Shigenari Jin‐Quan Yu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(22):6645-6649
An intermolecular C(sp3) H amination using a Pd0/PAr3 catalyst was developed. The reaction begins with oxidative addition of R2N OBz to a Pd0/PAr3 catalyst and subsequent cleavage of a C(sp3) H bond by the generated Pd NR2 intermediate. The catalytic cycle proceeds without the need for external oxidants in a similar manner to the extensively studied palladium(0)‐catalyzed C H arylation reactions. The electron‐deficient triarylphosphine ligand is crucial for this C(sp3) H amination reaction to occur. 相似文献
17.
Dr. Xuesong Wu Yan Zhao Dr. Guangwu Zhang Prof. Dr. Haibo Ge 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(14):3780-3784
The intramolecular dehydrogenative amidation of aliphatic amides, directed by a bidentate ligand, was developed using a copper‐catalyzed sp3 C H bond functionalization process. The reaction favors predominantly the C H bonds of β‐methyl groups over the unactivated methylene C H bonds. Moreover, a preference for activating sp3 C H bonds of β‐methyl groups, via a five‐membered ring intermediate, over the aromatic sp2 C H bonds was also observed in the cyclometalation step. Additionally, sp3 C H bonds of unactivated secondary sp3 C H bonds could be functionalized by favoring the ring carbon atoms over the linear carbon atoms. 相似文献
18.
Dr. Xuesong Wu Yan Zhao Dr. Guangwu Zhang Prof. Dr. Haibo Ge 《Angewandte Chemie (International ed. in English)》2014,53(14):3706-3710
The intramolecular dehydrogenative amidation of aliphatic amides, directed by a bidentate ligand, was developed using a copper‐catalyzed sp3 C? H bond functionalization process. The reaction favors predominantly the C? H bonds of β‐methyl groups over the unactivated methylene C? H bonds. Moreover, a preference for activating sp3 C? H bonds of β‐methyl groups, via a five‐membered ring intermediate, over the aromatic sp2 C? H bonds was also observed in the cyclometalation step. Additionally, sp3 C? H bonds of unactivated secondary sp3 C? H bonds could be functionalized by favoring the ring carbon atoms over the linear carbon atoms. 相似文献
19.
Phenyltrimethylammonium Salts as Methylation Reagents in the Nickel‐Catalyzed Methylation of C−H Bonds
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Takeshi Uemura Mao Yamaguchi Prof. Dr. Naoto Chatani 《Angewandte Chemie (International ed. in English)》2016,55(9):3162-3165
Methylation of C(sp2)?H bonds was achieved through the NiII‐catalyzed reaction of benzamides with phenyltrimethylammonium bromide or iodide as the source of the methyl group. The reaction has a broad scope and shows high functional‐group compatibility. The reaction is also applicable to the methylation of C(sp3)?H bonds in aliphatic amides. 相似文献
20.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(52):16872-16876
A rhodium(II)‐catalyzed reaction of newly prepared 4‐acyl‐1‐sulfonyl‐1,2,3‐triazoles with benzene, and its derivatives, is investigated. Acceptor/acceptor carbenoids generated from 4‐acyltriazoles undergo selective insertion at aromatic C(sp2)−H bonds in the presence of benzylic C(sp3)−H bonds to produce N ‐sulfonylenaminones. 相似文献