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1.
Haoquan Li Dr. Helfried Neumann Prof. Dr. Matthias Beller 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(29):10050-10056
A benign and efficient palladium‐catalyzed aminocarbonylation reaction of allylic alcohols is presented. The generality of this novel process is demonstrated by the synthesis of β,γ‐unsaturated amides including aliphatic, cinnamyl, and terpene derivatives. The choice of ligand is crucial for optimal carbonylation processes: Whereas in most cases the combination of PdCl2 with Xantphos ( L6 ) gave best results, sterically hindered substrates performed better in the presence of simple triphenylphosphine ( L10 ), and primary anilines gave the best results using cataCXium® PCy ( L8 ). The reactivity of the respective catalyst system is significantly enhanced by addition of small amounts of water. Mechanistic studies and control experiments revealed a tandem allylic alcohol amination/C?N bond carbonylation reaction sequence. 相似文献
2.
Cover Picture: Mild and Low‐Pressure fac‐Ir(ppy)3‐Mediated Radical Aminocarbonylation of Unactivated Alkyl Iodides through Visible‐Light Photoredox Catalysis (Chem. Eur. J. 27/2016) 下载免费PDF全文
3.
《Mendeleev Communications》2022,32(6):804-806
Methoxycarbonylation of styrene in the presence of homogeneous Ru catalysts is reported for the first time. Available Ru3(CO)12 together with halide source such as [bmim]Br, NaBr or LiCl represents active and easy to handle methoxycarbonylation catalyst. The key advantage of the new catalytic systems over traditional Pd catalysts is their high activity at CO pressure as low as 5 bar. 相似文献
4.
Yang Yuan Fu-Peng Wu Jian-Xing Xu Prof. Dr. Xiao-Feng Wu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(39):17203-17209
We report here a general four-component synthetic procedure for the preparation of β-boryl ketones and β-boryl vinyl esters. Joint catalyzed by palladium and copper catalysts, borocarbonylative reaction between vinylarenes, aryl halides/triflates, B2Pin2, and carbon monoxide proceed successfully. A variety of synthetically useful β-boryl ketones were synthesized in good to high yields by using aryl iodides as the substrates. It is noteworthy that when aryl triflates were applied as the starting materials, β-boryl vinyl esters were synthesized in a similar manner and with broad functional group tolerance. A rational mechanism for this reaction was also proposed. 相似文献
5.
Tomáš Čarný Dr. Ronan Rocaboy Dr. Antonin Clemenceau Prof. Dr. Olivier Baudoin 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(43):19142-19146
The 1,4-palladium shift strategy allows the functionalization of remote C−H bonds that are difficult to reach directly. Reported here is a domino reaction proceeding by C(sp3)−H activation, 1,4-palladium shift, and amino- or alkoxycarbonylation, which generates a variety of amides and esters bearing a quaternary β-carbon atom. Mechanistic studies showed that the aminocarbonylation of the σ-alkylpalladium intermediate arising from the palladium shift is fast using PPh3 as the ligand, and leads to the amide rather than the previously reported indanone product. 相似文献
6.
Fanni Bede Prof. Dr. László Kollár Dr. Nándor Lambert Prof. Dr. Péter Huszthy Dr. Péter Pongrácz 《European journal of organic chemistry》2023,26(31):e202300571
Palladium-catalyzed hydroaminocarbonylation reactions of olefins using aliphatic amines were performed under carbon monoxide atmosphere. Despite the strong basicity of the applied nucleophiles, the targeted amides were successfully synthesized in the absence of acidic additives. Styrene, oct-1-ene and isoprene were transformed to the corresponding amide isomers in moderate to good isolated yields under optimized reaction conditions. Various aliphatic amines were used as N-nucleophiles. The effect of chiral diphosphines on product distribution, that is, on chemo-, regio- and enantioselectivities was also studied. Plausible explanation was given for the additive-free hydroaminocarbonylation reaction. 相似文献
7.
Asymmetric Synthesis of Fluorinated Isoindolinones through Palladium‐Catalyzed Carbonylative Amination of Enantioenriched Benzylic Carbamates 下载免费PDF全文
Dr. Pablo Barrio Ignacio Ibáñez Lidia Herrera Dr. Raquel Román Dr. Silvia Catalán Prof. Dr. Santos Fustero 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(32):11579-11584
The asymmetric synthesis of fluorinated isoindolinones has been achieved by a palladium‐catalyzed aminocarbonylation reaction of the corresponding α‐fluoroalkyl o‐iodobenzylamines. A base‐mediated anti β‐hydride elimination process was suggested to explain the partial erosion of the optical purity observed in some cases. This mechanistic rationale enabled the minimization of this partial racemization by fine‐tuning the pKa of the base. 相似文献
8.
A Practical and General Base‐Catalyzed Carbonylation of Amines for the Synthesis of N‐Formamides 下载免费PDF全文
Dr. Wanfang Li Prof. Dr. Xiao‐Feng Wu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(42):14943-14948
A highly practical and general base‐catalyzed carbonylation of amines to the corresponding N‐formamides has been realized. Cheap inorganic bases, including Group IA and IIA metal hydroxides, alkoxides, carbonates, and phosphates, were effective catalysts for the transformation. In the presence of 10–40 mol % of KOH or K2CO3, various amines were converted into the corresponding N‐formamides in good‐to‐excellent yields using CO as the formylation reagents. 相似文献
9.
A Convenient Palladium‐Catalyzed Carbonylative Suzuki Coupling of Aryl Halides with Formic Acid as the Carbon Monoxide Source 下载免费PDF全文
Dr. Xinxin Qi Li‐Bing Jiang Hao‐Peng Li Prof. Dr. Xiao‐Feng Wu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(49):17650-17656
A practical palladium‐catalyzed carbonylative Suzuki coupling of aryl halides under carbon monoxide gas‐free conditions has been developed. Here, formic acid was utilized as the carbon monoxide source for the first time with acetic anhydride as the additive. A variety of diarylketones were produced in moderate to excellent yields from the corresponding aryl halides and arylboronic acids. 相似文献
10.
Jun Ren Jinzhou Yang Wei Wang Hailong Guo Zhijun Zuo Jianying Lin Zhong Li 《International journal of quantum chemistry》2015,115(13):853-858
The activity and selectivity of heterogeneous catalysts can be significantly improved by dispersion of another active component in the metal substrate. The impact of Rh promoter on the formation of dimethyl carbonate (DMC) via oxidative carbonylation of methanol on Cu–Rh/AC (activated carbon) catalyst was investigated by density functional theory calculations. The most stable configurations of reacting species (CO, OH, CH3O, monomethyl carbonate, and DMC) adsorbed on the Cu0(zero‐valent copper)/AC and Cu–Rh/AC surfaces were determined on the basis of the calculated results. The reaction energy and activation energy of the rate‐limiting steps on the Cu–Rh/AC and Cu0/AC surfaces were compared. The activation energies of the rate‐limiting step of CO insertion into dimethoxide are 206.3 and 304.8 kJ mol?1 on the Cu–Rh/AC and Cu0/AC surfaces, respectively. The activation energies of the rate‐limiting step of CO insertion into methoxide are 78.5 and 92.7 kJ/mol on the Cu–Rh/AC and Cu0/AC surfaces, respectively. The calculated results indicate that the addition of Rh atom has a significant effect on decreasing the active energy the main pathway for DMC formation. © 2015 Wiley Periodicals, Inc. 相似文献