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1.
Zhen Wang Jizhi Ni Prof. Dr. Yoichiro Kuninobu Prof. Dr. Motomu Kanai 《Angewandte Chemie (International ed. in English)》2014,53(13):3496-3499
The first copper‐catalyzed intramolecular C(sp3)? H and C(sp2)? H oxidative amidation has been developed. Using a Cu(OAc)2 catalyst and an Ag2CO3 oxidant in dichloroethane solvent, C(sp3)? H amidation proceeded at a terminal methyl group, as well as at the internal benzylic position of an alkyl chain. This reaction has a broad substrate scope, and various β‐lactams were obtained in excellent yield, even on gram scale. Use of CuCl2 and Ag2CO3 under an O2 atmosphere in dimethyl sulfoxide, however, leads to 2‐indolinone selectively by C(sp2)? H amidation. Kinetic isotope effect (KIE) studies indicated that C? H bond activation is the rate‐determining step. The 5‐methoxyquinolyl directing group could be removed by oxidation. 相似文献
2.
Dr. Qing Gu Dr. Hamad H. Al Mamari M. Sc. Karolina Graczyk Emelyne Diers Prof. Dr. Lutz Ackermann 《Angewandte Chemie (International ed. in English)》2014,53(15):3868-3871
Modular 1,2,3‐triazoles enabled iron‐catalyzed C? H arylations with broad scope. The novel triazole‐based bidentate auxiliary is easily accessible in a highly modular fashion and allowed for user‐friendly iron‐catalyzed C(sp2)? H functionalizations of arenes and alkenes with excellent chemo‐ and diastereoselectivities. The versatile iron catalyst also proved applicable for challenging C(sp3)? H functionalizations, and proceeds by an organometallic mode of action. The triazole‐assisted C? H activation strategy occurred under remarkably mild reaction conditions, and the auxiliary was easily removed in a traceless fashion. Intriguingly, the triazole group proved superior to previously used auxiliaries. 相似文献
3.
Dr. Xuesong Wu Yan Zhao Prof. Dr. Haibo Ge 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(31):9530-9533
Intramolecular dehydrogenative cyclization of aliphatic amides was achieved on unactivated sp3 carbon atoms by a nickel‐catalyzed C?H bond functionalization process with the assistance of a bidentate directing group. The reaction favors the C?H bonds of β‐methyl groups over the γ‐methyl or β‐methylene groups. Additionally, a predominant preference for the β‐methyl C?H bonds over the aromatic sp2 C?H bonds was observed. Moreover, this process also allows for the effective functionalization of benzylic secondary sp3 C?H bonds. 相似文献
4.
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
5.
Synthesis of Pyrrolophenanthridine Alkaloids Based on C(sp3)H and C(sp2)H Functionalization Reactions
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Dr. Chihiro Tsukano Nobusuke Muto Iderbat Enkhtaivan Prof. Yoshiji Takemoto 《化学:亚洲杂志》2014,9(9):2628-2634
Assoanine, pratosine, hippadine, and dehydroanhydrolycorine belong to the pyrrolophenanthridine family of alkaloids, which are isolated from plants of the Amaryllidaceae species. Structurally, these alkaloids are characterized by a tetracyclic skeleton that contains a biaryl moiety and an indole core, and compounds belonging to this class have received considerable interest from researchers in a number of fields because of their biological properties and the challenges associated with their synthesis. Herein, a strategy for the total synthesis of these alkaloids by using C? H activation chemistry is described. The tetracyclic skeleton was constructed in a stepwise manner by C(sp3)? H functionalization followed by a Catellani reaction, including C(sp2)? H functionalization. A one‐pot reaction involving both C(sp3)? H and C(sp2)? H functionalization was also attempted. This newly developed strategy is suitable for the facile preparation of various analogues because it uses simple starting materials and does not require protecting groups. 相似文献
6.
The site‐selective acyloxylation of aliphatic amides was achieved via a copper‐promoted C(sp3)? H bond functionalization process directed by a bidentate ligand. The reaction showed a great preference for activating C? H bonds of β‐methyl groups over those of γ‐methyl and unactivated methylene groups. 相似文献
7.
Asymmetric Organocatalytic Direct C(sp2)H/C(sp3)H Oxidative Cross‐Coupling by Chiral Iodine Reagents
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Hua Wu Yu‐Ping He Lue Xu Dong‐Yang Zhang Prof. Liu‐Zhu Gong 《Angewandte Chemie (International ed. in English)》2014,53(13):3466-3469
An asymmetric organocatalytic direct C? H/C? H oxidative coupling reaction of N1,N3‐diphenylmalonamides has been well established by using chiral organoiodine compounds as catalysts, wherein four C? H bonds were stereoselectively functionalized to give structurally diverse spirooxindoles with high levels of enantioselectivity. More importantly, the findings indicated that chiral hypervalent organoiodine reagents can serve as alternative catalysts for the creation of enantioselective functionalization of inactive C? H bonds. 相似文献
8.
Dr. Antonio Zucca Dr. Luca Maidich Laura Canu Dr. Giacomo L. Petretto Prof. Sergio Stoccoro Prof. Maria Agostina Cinellu Dr. Guy J. Clarkson Dr. Jonathan P. Rourke 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(18):5501-5510
Rollover cyclometalation involves bidentate heterocyclic donors, unusually acting as cyclometalated ligands. The resulting products, possessing a free donor atom, react differently from the classical cyclometalated complexes. Taking advantage of a “rollover”/“retro‐rollover” reaction sequence, a succession of oxidative addition and reductive elimination in a series of platinum(II) complexes [Pt(N,C)(Me)(PR3)] resulted in a rare C(sp2)?C(sp3) bond formation to give the bidentate nitrogen ligands 3‐methyl‐2,2′‐bipyridine, 3,6‐dimethyl‐2,2′‐bipyridine, and 3‐methyl‐2‐(2′‐pyridyl)‐quinoline, which were isolated and characterized. The nature of the phosphane PR3 is essential to the outcome of the reaction. This route constitutes a new method for the activation and functionalization of C?H bond in the C(3) position of bidentate heterocyclic compounds, a position usually difficult to functionalize. 相似文献
9.
Iridium Complexes Containing Mesoionic C Donors: Selective C(sp3)H versus C(sp2)H Bond Activation,Reactivity Towards Acids and Bases,and Catalytic Oxidation of Silanes and Water
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Ana Petronilho James A. Woods Helge Mueller‐Bunz Stefan Bernhard Martin Albrecht 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(48):15775-15784
Metalation of a C2‐methylated pyridylimidazolium salt with [IrCp*Cl2]2 affords either an ylidic complex, resulting from C(sp3)?H bond activation of the C2‐bound CH3 group if the metalation is performed in the presence of a base, such as AgO2 or Na2CO3, or a mesoionic complex via cyclometalation and thermally induced heterocyclic C(sp2)?H bond activation, if the reaction is performed in the absence of a base. Similar cyclometalation and complex formation via C(sp2)?H bond activation is observed when the heterocyclic ligand precursor consists of the analogous pyridyltriazolium salt, that is, when the metal bonding at the C2 position is blocked by a nitrogen rather than a methyl substituent. Despite the strongly mesoionic character of both the imidazolylidene and the triazolylidene, the former reacts rapidly with D+ and undergoes isotope exchange at the heterocyclic C5 position, whereas the triazolylidene ligand is stable and only undergoes H/D exchange under basic conditions, where the imidazolylidene is essentially unreactive. The high stability of the Ir?C bond in aqueous solution over a broad pH range was exploited in catalytic water oxidation and silane oxidation. The catalytic hydrosilylation of ketones proceeds with turnover frequencies as high as 6 000 h?1 with both the imidazolylidene and the triazolylidene system, whereas water oxidation is enhanced by the stronger donor properties of the imidazol‐4‐ylidene ligands and is more than three times faster than with the triazolylidene analogue. 相似文献
10.
Transition Metal‐Catalyzed Carbonylative CH Bond Functionalization of Arenes and C(sp3)H Bond of Alkanes
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Sandip T. Gadge Prashant Gautam Bhalchandra M. Bhanage 《Chemical record (New York, N.Y.)》2016,16(2):835-856
In this article, we present the progress made in the area of carbonylative C? H functionalization, with special emphasis on arenes and alkanes. The importance of directing group assistance and C? H functionalization using CO surrogates is also included. The budding development in the area of transition metal‐catalyzed C(sp3)? H activation makes us feel it necessary to file a summary on the past, as well as current, contributions and a prospective outlook on the transition metal‐catalyzed carbonylative transformation of C? H bonds, which is the focus of this review. 相似文献
11.
Chiral Counteranion Strategy for Asymmetric Oxidative C(sp3)H/C(sp3)H Coupling: Enantioselective α‐Allylation of Aldehydes with Terminal Alkenes
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Pu‐Sheng Wang Hua‐Chen Lin Yu‐Jia Zhai Zhi‐Yong Han Prof. Dr. Liu‐Zhu Gong 《Angewandte Chemie (International ed. in English)》2014,53(45):12218-12221
The first enantioselective α‐allylation of aldehydes with terminal alkenes has been realized by combining asymmetric counteranion catalysis and palladium‐catalyzed allylic C? H activation. This method can tolerate a wide scope of α‐branched aromatic aldehydes and terminal alkenes, thus affording allylation products in high yields and with good to excellent levels of enantioselectivity. Importantly, the findings suggest a new strategy for the future creation of enantioselective C? H/C? H coupling reactions. 相似文献
12.
The catalytic cross‐dehydrogenative coupling (CDC) reaction has received intense attention in recent years. The attractive feature of this coupling process is the formation of a C? C bond from two C? H moieties under oxidative conditions. In this Focus Review, recent advances in the palladium‐catalyzed CDC reactions of C(sp2)? H bond are summarized, with a focus on the period from 2011 to early 2013. 相似文献
13.
Easily Accessible Auxiliary for Palladium‐Catalyzed Intramolecular Amination of C(sp2)H and C(sp3)H Bonds at δ‐ and ε‐Positions
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Chao Wang Changpeng Chen Jingyu Zhang Jian Han Qian Wang Kun Guo Pei Liu Mingyu Guan Dr. Yingming Yao Prof. Dr. Yingsheng Zhao 《Angewandte Chemie (International ed. in English)》2014,53(37):9884-9888
An easily synthesized and accessible N,O‐bidentate auxiliary has been developed for selective C? H activation under palladium catalysis. The novel auxiliary showed its first powerful application in C? H functionalization of remote positions. Both C(sp2)? H and C(sp3)? H bonds at δ‐ and ε‐positions were effectively activated, thus giving tetrahydroquinolines, benzomorpholines, pyrrolidines, and indolines in moderate to excellent yields by palladium‐catalyzed intramolecular C? H amination. 相似文献
14.
Gold‐Catalyzed C(sp3)H/C(sp)H Coupling/Cyclization/Oxidative Alkynylation Sequence: A Powerful Strategy for the Synthesis of 3‐Alkynyl Polysubstituted Furans
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Yuanhong Ma Shuai Zhang Shiping Yang Dr. Feijie Song Prof. Dr. Jingsong You 《Angewandte Chemie (International ed. in English)》2014,53(30):7870-7874
In sharp contrast to the gold‐catalyzed reactions of alkynes/allenes with nucleophiles, gold‐catalyzed oxidative cross‐couplings and especially C? H/C? H cross‐coupling have been under represented. By taking advantage of the unique redox property and carbophilic π acidity of gold, this work realizes the first gold‐catalyzed direct C(sp3)? H alkynylation of 1,3‐dicarbonyl compounds with terminal alkynes under mild reaction conditions, with subsequent cyclization and in situ oxidative alkynylation. A variety of terminal alkynes including aryl, heteroaryl, alkenyl, alkynyl, alkyl, and cyclopropyl alkynes all successfully participate in the domino reaction. The protocol offers a simple and region‐defined approach to 3‐alkynyl polysubstituted furans. 相似文献
15.
Jian He Heng Jiang Ryosuke Takise Ru‐Yi Zhu Dr. Gang Chen Prof. Dr. Hui‐Xiong Dai Dr. T. G. Murali Dhar Dr. Jun Shi Dr. Hao Zhang Dr. Peter T. W. Cheng Prof. Dr. Jin‐Quan Yu 《Angewandte Chemie (International ed. in English)》2016,55(2):785-789
A quinoline‐based ligand effectively promotes the palladium‐catalyzed borylation of C(sp3)? H bonds. Primary β‐C(sp3)? H bonds in carboxylic acid derivatives as well as secondary C(sp3)? H bonds in a variety of carbocyclic rings, including cyclopropanes, cyclobutanes, cyclopentanes, cyclohexanes, and cycloheptanes, can thus be borylated. This directed borylation method complements existing iridium(I)‐ and rhodium(I)‐catalyzed C? H borylation reactions in terms of scope and operational conditions. 相似文献
16.
Dr. Bingwei Zhou Yuanyuan Hu Prof. Dr. Congyang Wang 《Angewandte Chemie (International ed. in English)》2015,54(46):13659-13663
Herein, a manganese‐catalyzed nucleophilic addition of inert C(sp2)? H bonds to aldehydes and nitriles is disclosed by virtue of a dual activation strategy. The reactions feature mild reaction conditions, excellent regio‐ and stereoselectivity, and a wide substrate scope, which includes both aromatic and olefinic C? H bonds, as well as a large variety of aldehydes and nitriles. Moreover, mechanistic studies shed light on possible catalytic cycles. 相似文献
17.
Palladium–N‐Heterocyclic Carbene (NHC)‐Catalyzed Asymmetric Synthesis of Indolines through Regiodivergent C(sp3)H Activation: Scope and DFT Study
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Dmitry Katayev Dr. Evgeny Larionov Dr. Masafumi Nakanishi Dr. Céline Besnard Prof. Dr. E. Peter Kündig 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(46):15021-15030
Two bulky, chiral, monodentate N‐heterocyclic carbene ligands were applied to palladium‐catalyzed asymmetric C?H arylation to incorporate C(sp3)?H bond activation. Racemic mixtures of the carbamate starting materials underwent regiodivergent reactions to afford different trans‐2,3‐substituted indolines. Although this CAr?Calkyl coupling requires high temperatures (140–160 °C), chiral induction is high. This regiodivergent reaction, when carried out with enantiopure starting materials, can lead to single structurally different enantiopure products, depending on the catalyst chirality. The C?H activation at a tertiary center was realized only in the case of a cyclopropyl group. No C?H activation takes place alpha to a tertiary center. A detailed DFT study is included and analyses of methyl versus methylene versus methine C?H activation is used to rationalize experimentally observed regio‐ and enantioselectivities. 相似文献
18.
Rhodium(I)‐Catalyzed Sequential C(sp)C(sp3) and C(sp3)C(sp3) Bond Formation through Migratory Carbene Insertion
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Ying Xia Sheng Feng Zhen Liu Dr. Yan Zhang Prof. Dr. Jianbo Wang 《Angewandte Chemie (International ed. in English)》2015,54(27):7891-7894
A RhI‐catalyzed three‐component reaction of tert‐propargyl alcohol, diazoester, and alkyl halide has been developed. This reaction can be considered as a carbene‐involving sequential alkyl and alkynyl coupling, in which C(sp)? C(sp3) and C(sp3)? C(sp3) bonds are built successively on the carbenic carbon atom. The RhI‐carbene migratory insertion of an alkynyl moiety and subsequent alkylation are proposed to account for the two separate C? C bond formations. This reaction provides an efficient and tunable method for the construction of all‐carbon quaternary center. 相似文献
19.
Lin‐Bao Zhang Dr. Xin‐Qi Hao Shou‐Kun Zhang Zhan‐Jiang Liu Xin‐Xiang Zheng Dr. Jun‐Fang Gong Dr. Jun‐Long Niu Prof. Mao‐Ping Song 《Angewandte Chemie (International ed. in English)》2015,54(1):272-275
The cobalt‐catalyzed alkoxylation of C(sp2)? H bonds in aromatic and olefinic carboxamides has been developed. The reaction proceeded under mild conditions in the presence of Co(OAc)2?4H2O as the catalyst and tolerates a wide range of both alcohols and benzamide substrates, including even olefinic carboxamides. In addition, this reaction is the first example of the direct alkoxylation of alkenes through C? H bond activation. 相似文献
20.
Chemoselective Amination of Propargylic C(sp3)H Bonds by Cobalt(II)‐Based Metalloradical Catalysis
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Prof. Dr. Hongjian Lu Dr. Chaoqun Li Dr. Huiling Jiang Christopher L. Lizardi Prof. Dr. X. Peter Zhang 《Angewandte Chemie (International ed. in English)》2014,53(27):7028-7032
Highly chemoselective intramolecular amination of propargylic C(sp3)? H bonds has been demonstrated for N‐bishomopropargylic sulfamoyl azides through cobalt(II)‐based metalloradical catalysis. Supported by D2h‐symmetric amidoporphyrin ligand 3,5‐DitBu‐IbuPhyrin, the cobalt(II)‐catalyzed C? H amination proceeds effectively under neutral and nonoxidative conditions without the need of any additives, and generates N2 as the only byproduct. The metalloradical amination is suitable for both secondary and tertiary propargylic C? H substrates with an unusually high degree of functional‐group tolerance, thus providing a direct method for high‐yielding synthesis of functionalized propargylamine derivatives. 相似文献