72487-30-0Relevant articles and documents
Copper-Catalyzed 1,1-Boroalkylation of Terminal Alkynes: Access to Alkenylboronates via a Three-Component Reaction
Li, Ziyong,Sun, Jiangtao
supporting information, p. 3706 - 3711 (2021/05/31)
A copper-catalyzed three-component reaction of terminal alkynes, diazo compounds, and B2pin2 to prepare trisubstituted alkenylboronates has been developed. This difunctionalization of alkynes selectively occurs at the terminal carbon atom and proceeds via
Copper on charcoal: Cu0nanoparticle catalysed aerobic oxidation of α-diazo esters
Chu, Changhu,Dong, Wenwen,Lin, Jia,Teng, Jiangge,Wang, Zhiwei,Zhao, Rong
, p. 6120 - 6126 (2021/07/21)
By using a charcoal supported nano Cu0catalyst (Cu/C), a highly efficient oxidation of α-diazo esters to α-ketoesters with molecular oxygen as the sole oxidant has been developed. In the presence of the Cu/C catalyst, 2-aryl-α-diazo esters with both electron-donating and electron-withdrawing groups can be oxidized to the corresponding α-ketoesters efficiently. Furthermore, this Cu/C catalyst can catalyse the reaction of aryl α-diazo ester with water to form aryl ketoester, 2-aryl-2-hydroxyl acetate ester and 2-aryl acetate ester. In this case, water is split by α-diazo ester, and the diazo group is displaced by the oxygen or hydrogen atom in water. Mechanistic investigation showed that the reaction of α-diazo ester with oxygen proceeds through a radical pathway. In the presence of 2,2,6,6-tetramethyl piperidine nitrogen oxide, the reaction of α-diazo ester with oxygen is dramatically inhibited. Furthermore, the reaction of α-diazo ester with water is investigated by an isotopic tracer method, and GCMS detection showed that a disproportionation reaction occurred between α-diazo ester and water.
Blue Light-Promoted Formal [4+1]-Annulation of Diazoacetates with o-Aminoacetophenones: Synthesis of Polysubstituted Indolines and Computational Study
Chen, Jinzhou,Liu, Shuhao,Lv, Xinxin,Hong, Kemiao,Lei, Jinping,Xu, Xinfang,Hu, Wenhao
, p. 13920 - 13928 (2020/11/03)
A blue light-promoted formal [4+1]-annulation of diazoacetates with o-aminoacetophenones has been reported, which provides an environmentally friendly method for the synthesis of polysubstituted indoline derivatives in moderate to good yields with excellent diastereoselectivities. Detailed mechanistic studies through density functional theory calculations reveal that the (E)-enol species is the key intermediate in this transformation, and the excellent diastereoselectivity is enabled via H-bonding in the intramolecular Aldol-type addition.
A gold(i)-catalysed chemoselective three-component reaction between phenols, α-diazocarbonyl compounds and allenamides
Yu, Sifan,Chen, Jinzhou,Liu, Gengxin,Lei, Jinping,Hu, Wenhao,Qiu, Huang
supporting information, p. 1649 - 1652 (2020/02/18)
Gold(i) catalysts are considered to be efficient in promoting sp2 C-H bond insertion at the para position of unprotected phenols because of the exceptionally chemical reactivity of gold-stabilized carbophilic carbocations. Herein, we present a
Tridentate Nickel(II)-Catalyzed Chemodivergent C-H Functionalization and Cyclopropanation: Regioselective and Diastereoselective Access to Substituted Aromatic Heterocycles
Nag, Ekta,Gorantla, Sai Manoj N. V. T.,Arumugam, Selvakumar,Kulkarni, Aditya,Mondal, Kartik Chandra,Roy, Sudipta
, p. 6313 - 6318 (2020/09/02)
A Schiff-base nickel(II)-phosphene-catalyzed chemodivergent C-H functionalization and cyclopropanation of aromatic heterocycles is reported in moderate to excellent yields and very good regioselectivity and diastereoselectivity. The weak, noncovalent interaction between the phosphene ligand and Ni center facilitates the ligand dissociation, generating the electronically and coordinatively unsaturated active catalyst. The proposed mechanisms for the reported reactions are in good accord with the experimental results and theoretical calculations, providing a suitable model of stereocontrol for the cyclopropanation reaction.
Selective Vinylogous Reactivity of Carbene Intermediate in Gold-Catalyzed Alkyne Carbocyclization: Synthesis of Indenols
Zhang, Cheng,Li, Hongli,Pei, Chao,Qiu, Lihua,Hu, Wenhao,Bao, Xiaoguang,Xu, Xinfang
, p. 2440 - 2447 (2019/03/08)
A gold-catalyzed carbocyclization of alkynes with a pendant diazo group that is completed by reaction with a protic nucleophile for the synthesis of indenol derivatives with a tertiary center is described. Mechanistic studies and DFT calculations indicate
Planar chiral [2.2]paracyclophane-based bisoxazoline ligands and their applications in Cu-Mediated N-H insertion reaction
Knoll, Daniel M.,Hu, Yuling,Hassan, Zahid,Nieger, Martin,Br?se, Stefan
, (2019/11/20)
New catalysts for important C-N bond formation are highly sought after. In this work, we demonstrate the synthesis and viability of a new class of planar chiral [2.2]paracyclophane-based bisoxazoline (BOX) ligands for the copper-catalyzed N-H insertion of α-diazocarbonyls into anilines. The reaction features a wide substrate scope and moderate to excellent yields, and delivers the valuable products at ambient conditions.
Ketenimine Formation Catalyzed by a High-Valent Cobalt Carbene in Bulky Alkoxide Ligand Environment
Grass, Amanda,Dewey, Nicholas S.,Lord, Richard L.,Groysman, Stanislav
, p. 962 - 972 (2019/02/26)
High-valent cobalt carbene Co(OR)2(CPh2) (OR = OCtBu2Ph) undergoes reaction with various isocyanides CNR (CNR = 2,6-dimethylphenyl isocyanide, 4-methoxyphenyl isocyanide, 2-chloro-6-methylphenyl isocyanide, adamantyl isocyanide) to yield the corresponding ketenimine. The reaction is accompanied by the formation of cobalt bis(alkoxide) bis(isocyanide) complexes Co(OR)2(CNR)2, which were independently synthesized and characterized. DFT calculations suggest the mechanism proceeds through isocyanide binding to Co, followed by intramolecular insertion into the Co-carbene bond to form the ketenimine. We have also conducted an investigation of the catalytic formation of ketenimines at room temperature using mixtures of diazoalkanes (diphenyldiazomethane, methyl diazo(phenyl)acetate, and ethyl diazoacetate) and isocyanides (2,6-dimethylphenyl isocyanide, 4-methoxyphenyl isocyanide, adamantyl isocyanide, cyclohexyl isocyanide, and benzyl isocyanide). While no catalytic reactivity was observed for diphenyldiazomethane, ester-substituted diazoalkanes (diazoesters) demonstrate catalytic turnover. Relatively high yields are observed for the reactions involving bulkier aliphatic substrates adamantyl and cyclohexyl isocyanides. Mechanistic studies suggest that the lack of catalytic reactivity involving diphenyldiazomethane results from the inability of Co(OR)2(CNR)2 to undergo carbene formation upon reaction with N2CPh2. In contrast, facile reaction is observed between Co(OR)2(CNR)2 and diazoesters, which enables the overall catalytic reactivity.
Ru(II)-Catalyzed Cross-Coupling of Cyclopropenes with Diazo Compounds: Formation of Olefins from Two Different Carbene Precursors
Wang, Bo,Yi, Heng,Zhang, Hang,Sun, Tong,Zhang, Yan,Wang, Jianbo
, p. 1026 - 1032 (2018/01/28)
Formal carbene dimerization is a convergent method for the synthesis of alkenes. Herein, we report a Ru(II)-catalyzed carbene dimerization of cyclopropenes and diazo compounds. The yields are up to 97% and the stereoselectivity are up to >20:1. Mechanistically, it has been experimentally demonstrated that the catalyst reacts with cyclopropene first to generate a Ru(II)-carbene species, which is attacked by nucleophilic diazo substrate, followed by dinitrogen extrusion to form the double bond.
Stereoselective Synthesis of Tetrasubstituted Furylalkenes via Gold-Catalyzed Cross-Coupling of Enynones with Diazo Compounds
Liu, Pei,Sun, Jiangtao
, p. 3482 - 3485 (2017/07/15)
A stereoselective, gold-catalyzed, cross-coupling reaction of enynones with diazo compounds has been developed, affording 2-alkenylfurans in moderate to good yields with excellent E-stereoselectivity. Upon using diazo compounds as nucleophiles to trap the in situ formed gold furyl carbene, this protocol provides a novel path toward the formation of unsymmetrical tetrasubstituted alkenes.
