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51.
Facile Insertion of Carbon Dioxide into Cu2(μ‐H) Dinuclear Units Supported by Tetraphosphine Ligands
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Kanako Nakamae Dr. Bunsho Kure Prof. Takayuki Nakajima Prof. Yasuyuki Ura Prof. Tomoaki Tanase 《化学:亚洲杂志》2014,9(11):3106-3110
Reactions of meso‐bis[(diphenylphosphinomethyl)phenylphosphino]methane (dpmppm) with CuI species in the presence of NaBH4 afforded di‐ and tetranuclear copper hydride complexes, [Cu2(μ‐H)(μ‐dpmppm)2]X ( 1 ) and [Cu4(μ‐H)2(μ4‐H)(μ‐dpmppm)2]X ( 2 ) (X=BF4, PF6). Complex 1 undergoes facile insertion of CO2 (1 atm) at room temperature, leading to a formate‐bridged dicopper complex [Cu2(μ‐HCOO)(dpmppm)2]X ( 3 ). The experimental and DFT theoretical studies clearly demonstrate that CO2 insertion into the Cu2(μ‐H) unit occurred with the flexible dicopper platform. Complex 2 also undergoes CO2 insertion to give a formate‐bridged complex, [Cu4(μ‐HCOO)3(dpmppm)2]X, during which the square Cu4 framework opened up to a linear tetranuclear chain. 相似文献
52.
Constanze Keck Dr. Jennifer Hahn Divanshu Gupta Prof. Dr. Holger F. Bettinger 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(5):e202103614
The boron-nitrogen analogue of ortho-benzyne, 1,2-azaborinine, is a reactive intermediate that features a formal boron-nitrogen triple bond. We here show by combining experimental and computational techniques that the Lewis acidity of the boron center of dibenzo[c,e][1,2]azaborinine allows interaction with the silicon containing single bonds Si−E through the silicon bonding partner E (E=F, Cl, OR, H). The binding to boron activates the Si−E bonds for subsequent insertion reaction. This shows that the BN-aryne is a ferocious species that even can activate and insert into the very strong Si−F bond. 相似文献
53.
Asymmetric NH Insertion of Secondary and Primary Anilines under the Catalysis of Palladium and Chiral Guanidine Derivatives
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Yin Zhu Prof. Dr. Xiaohua Liu Dr. Shunxi Dong Yuhang Zhou Wei Li Dr. Lili Lin Prof. Dr. Xiaoming Feng 《Angewandte Chemie (International ed. in English)》2014,53(6):1636-1640
Efficient enantioselective N? H insertion reactions of secondary and primary anilines were catalyzed by palladium(0) in combination with chiral guanidine derivatives. A broad range of substituted anilines were tolerated, and the corresponding products were obtained in high yield (up to 99 %) with good enantioselectivity (up to 94 % ee) under mild reaction conditions. The N? H insertion mechanism was examined by the study of kinetic isotope effects, control experiments, HRMS, and spectroscopic analysis. 相似文献
54.
Rhodium(III)‐Catalyzed ortho Alkenylation of N‐Phenoxyacetamides with N‐Tosylhydrazones or Diazoesters through CH Activation
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Fangdong Hu Ying Xia Fei Ye Zhenxing Liu Prof. Dr. Chen Ma Prof. Dr. Yan Zhang Prof. Dr. Jianbo Wang 《Angewandte Chemie (International ed. in English)》2014,53(5):1364-1367
A coupling reaction of N‐phenoxyacetamides with N‐tosylhydrazones or diazoesters through RhIII‐catalyzed C? H activation is reported. In this reaction, ortho‐alkenyl phenols were obtained in good yields and with excellent regio‐ and stereoselectivity. Rh–carbene migratory insertion is proposed as the key step in the reaction mechanism. 相似文献
55.
Erica D. Couch Dr. Tyler J. Auvil Prof. Anita E. Mattson 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(27):8283-8287
The enhanced catalytic activity of difluoroboronate ureas proved to be essential as an acidity amplifier to promote metal‐free O?H and S?H insertion reactions of α‐aryldiazoacetates in high yield. This methodology was found to be generally applicable to a broad substrate scope and presents a conceptually new approach for organocatalytic diazo insertion reactions. Mechanistic investigations suggest that the reaction pathway involves a urea‐induced protonation of the α‐aryldiazoester. 相似文献
56.
Andreas Wolfgang Kyri Dr. Vitaly Nesterov Dr. Gregor Schnakenburg Prof. Dr. Rainer Streubel 《Angewandte Chemie (International ed. in English)》2014,53(40):10809-10812
While PV 1,2‐oxaphosphetanes are well known from the Wittig reaction, their PIII analogues are still unexplored. Herein, the synthesis and reactions of the first 1,2‐oxaphosphetane complexes are presented, which were achieved by reaction of the phosphinidenoid complex [Li(12‐crown‐4)(solv)][(OC)5W{(Me3Si)2HCPCl}] with different epoxides. The title compounds appeared to be stable in toluene up to 100 °C, before unselective decomposition started. Acid‐induced ring expansion with benzonitrile resulted in selective formation of the first complex bearing a 1,3,4‐oxazaphosphacyclohex‐2‐ene ligand. 相似文献
57.
Derek C. Church Jonathan K. Pokorski 《Angewandte Chemie (International ed. in English)》2020,59(28):11379-11383
Cell‐based therapies are gaining prominence in treating a wide variety of diseases and using synthetic polymers to manipulate these cells provides an opportunity to impart function that could not be achieved using solely genetic means. Herein, we describe the utility of functional block copolymers synthesized by ring‐opening metathesis polymerization (ROMP) that can insert directly into the cell membrane via the incorporation of long alkyl chains into a short polymer block leading to non‐covalent, hydrophobic interactions with the lipid bilayer. Furthermore, we demonstrate that these polymers can be imbued with advanced functionalities. A photosensitizer was incorporated into these polymers to enable spatially controlled cell death by the localized generation of 1O2 at the cell surface in response to red‐light irradiation. In a broader context, we believe our polymer insertion strategy could be used as a general methodology to impart functionality onto cell‐surfaces. 相似文献
58.
Mami Miyairi Tsuyoshi Taniguchi Tatsuya Nishimura Katsuhiro Maeda 《Angewandte Chemie (International ed. in English)》2020,59(35):14772-14780
An alternative reaction mechanism of the polymerization of diphenylacetylelnes using a catalytic system composed of tungsten(VI) chloride and tetraphenyltin has been proposed through the optimization of reaction conditions and investigation of the effect of the electronic nature of diphenylacetylene monomers on the polymerizability. The detailed structures of the polymers have been suggested by mass spectrometric analysis of the obtained polymers and oligomers, which suggested that a phenyl group of tetraphenyltin has been introduced to an initiating end of the polymer chain. Mass spectrometric analysis also provided information about the termination processes of the polymerization. The experimental results strongly suggested that the polymerization of diphenylacetylenes using tungsten(VI) chloride and tetraphenyltin proceeds through a migratory insertion mechanism rather than the long‐accepted metathesis mechanism. 相似文献
59.
Robert D. Barrows Mark J. Dresel Thomas J. Emge Paul R. Rablen Spencer Knapp 《Molecules (Basel, Switzerland)》2022,27(1)
The amidation reaction of a tetrahydroisoquinolin-1-one-4-carboxylic acid is a key step in the multi-kilogram-scale preparation of the antimalarial drug SJ733, now in phase 2 clinical trials. In the course of investigating THIQ carboxamidations, we found that propanephosphonic acid anhydride (T3P) is an effective reagent, although the yield and byproducts vary with the nature and quantity of the base. As a control, the T3P reaction of a 3-(2-thienyl) THIQ was performed in the absence of the amine, and the products were characterized: among them are three dimeric allenes and two dimeric lactones. A nucleophile-promoted ketene dimerization process subject to subtle steric and stereoelectronic effects accounts for their formation. Two novel monomeric products, a decarboxylated isoquinolone and a purple, fused aryl ketone, were also isolated, and mechanisms for their formation from the ketene intermediate are proposed. 相似文献
60.