2170-06-1Relevant articles and documents
Reactions of in situ generated (η2-phenyltrimethylsilylacetylene)zirconocene
Erker, Gerhard,Zwettler, Roland
, p. 179 - 188 (1991)
The five-membered metallacycle (1, R1 = SiMe3, R2 = Ph) is a suitable starting material for the in situ generation of the reactive (η2-phenyltrimethylsilylethyne)zirconocene (3).Thus, thermolysis of 1 (70 deg C) with trimethylphosphane gives Cp2Zr(Me3SiCCPh)(PMe3) (8) and free Me3SiCCPh (4).Subsequent reaction of 8 with acetophenone produces (9, R1 = SiMe3, R2 = Ph).Thermolysis of 1 in the presence of CpW(CO)3H also results in the liberation of one equivalent of 4.The reactive intermediate 3 is protonated to giveCp2Zr(CR1=CHR2)(μ-OC)W(CO)2Cp (12, R1 = SiMe3, R2 = Ph).Treatment of 1 with in acetonitrile gives the cationic (13a: R1 = SiMe3, R2 = Ph) and its regioisomer 13b (R1 and R2 exchanged).There is evidence that the complexes 13 are formed by acetonitrile addition to thermally-generated 3 to give , which is then subsequently protonated at the basic ring nitrogen.These reactions show that a readily available metallacyclopentadiene system can be used as a convenient synthetic equivalent of a very reactive (η2-alkyne)metallocene complex by thermally induced equilibration in the presence of suitable trapping reagents.
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Zakharkin et al.
, p. 881,886 (1965)
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Bimetallic nano-Pd/PdO/Cu system as a highly effective catalyst for the Sonogashira reaction
Korzec, Mateusz,Bartczak, Piotr,Niemczyk, Anna,Szade, Jacek,Kapkowski, Maciej,Zenderowska, Paulina,Balin, Katarzyna,Lelatko, Jozef,Polanski, Jaroslaw
, p. 1 - 8 (2014)
A copper-supported nanopalladium catalyst obtained by an innovative method of nanoparticle transfer from the intermediate carrier SiO2 to the target Cu carrier was a highly efficient and selective catalyst, giving as much as quantitative conver
A practical and efficient method for late-stage deuteration of terminal alkynes with silver salt as catalyst
Wu, Ding-Chuan,Bai, Jing-Wen,Guo, Lei,Hu, Guang-Qi,Liu, Kai-Hui,Sheng, Fei-Fei,Zhang, Hong-Hai,Sun, Zheng-Yi,Shen, Kang,Liu, Xiang
, (2021)
A practical and efficient H/D exchange method for selective deuteration of terminal alkynes was disclosed. The reaction was simply performed with CF3COOAg as catalyst at room temperature, affording products with high level of deuterium incorporation. The excellent site-selectivity and promising functional group tolerance of this protocol enabled deuteration of pharmaceuticals and nature product derivatives.
Formation and ligand-based reductive chemistry of bridged bis-alkylidene scandium(III) complexes
Ma, Wangyang,Yu, Chao,Chi, Yue,Chen, Tianyang,Wang, Lianjun,Yin, Jianhao,Wei, Baosheng,Xu, Ling,Zhang, Wen-Xiong,Xi, Zhenfeng
, p. 6852 - 6856 (2017)
The chemistry of rare-earth carbene and alkylidene complexes including their synthesis, structure and reaction is a challenging issue because of their high reactivity (or instability) and the lack of synthetic methods. In this work, we report the first synthesis of the bridged bis-alkylidene complexes which feature a 2-butene-1,1,4,4-tetraanion and four Sc-C(sp3) bonds by the reaction of 1,4-dilithio-1,3-butadienes with ScCl3. This reaction proceeds via two key intermediates: an isolable scandacyclopentadiene and a proposed scandacyclopropene. The scandacyclopentadiene undergoes β,β′-C-C bond cleavage to generate the scandacyclopropene, which then dimerizes to afford the bridged bis-alkylidene complex via a cooperative double metathesis reaction. Reaction chemistry study of the bridged bis-alkylidene complex reveals their ligand-based reduction reactivity towards different oxidants such as hexachloroethane, disulfide and cyclooctatetraene.
Synthesis, Characterization of Spirocyclic λ3-Iodanes and Their Application to Prepare 4,1-Benzoxazepine-2,5-diones and 1,3-Diynes
Sun, Xu,Guo, Xiao-Qiang,Chen, Lian-Mei,Kang, Tai-Ran
supporting information, p. 4312 - 4316 (2021/02/06)
Herein, a [3+2] cycloaddition of aza-oxyallylic cations with ethynylbenziodoxolones for synthesis of new λ3-iodanes containing spirocyclic 4-oxazolidinone has been developed. This cyclic λ3-iodanes display stability in air and excellent solubility in organic solvent. Using them as substrate, both the 4,1-benzoxazepine-2,5-diones and symmetrical 1,3-diynes derivatives were afforded in high yield under copper(I)-catalyzed conditions.
Site-Selective Csp3-Csp/Csp3-Csp2Cross-Coupling Reactions Using Frustrated Lewis Pairs
Dasgupta, Ayan,Stefkova, Katarina,Babaahmadi, Rasool,Yates, Brian F.,Buurma, Niklaas J.,Ariafard, Alireza,Richards, Emma,Melen, Rebecca L.
supporting information, p. 4451 - 4464 (2021/04/07)
The donor-acceptor ability of frustrated Lewis pairs (FLPs) has led to widespread applications in organic synthesis. Single electron transfer from a donor Lewis base to an acceptor Lewis acid can generate a frustrated radical pair (FRP) depending on the s
