16004-52-7Relevant academic research and scientific papers
Palladium-catalyzed intermolecular controlled insertion of benzyne- benzyne-alkene and benzyne-alkyne-alkene - Synthesis of phenanthrene and naphthalene derivatives
Yoshikawa, Eiji,Yamamoto, Yoshinori
, p. 173 - 175 (2000)
Aryne reagents, unlike alkynes, undergo insertion by allyl palladium complexes. The verification of the conversion described here is shown using Equation (1) as an example. The reaction proceeds in a few hours in refluxing acetonitrile to give the phenanthrene derivative in up to 71% yield.
Pd(II)-NHDC-Functionalized UiO-67 Type MOF for Catalyzing Heck Cross-Coupling and Intermolecular Benzyne-Benzyne-Alkene Insertion Reactions
Wei, Yong-Liang,Li, Yue,Chen, Yun-Qi,Dong, Ying,Yao, Jia-Jia,Han, Xin-Yue,Dong, Yu-Bin
, p. 4379 - 4386 (2018/04/25)
A novel palladium N-heterocyclic bis-carbene dicarboxylate ligand (Pd-NHDC-H2L) was successfully synthesized. In addition, an Pd-NHDC-containing UiO-67 type MOF (UiO-67-Pd-NHDC) was prepared on the basis of a size-matched ligand mixture of biphenyl-4,4′-dicarboxylic acid/Pd-NHDC-H2L (9/1) and ZrCl4 under solvothermal conditions. The obtained UiO-67-Pd-NHC MOF can be a highly heterogeneous catalyst to promote Heck cross-coupling and intermolecular benzyne-benzyne-alkene insertion reactions.
Palladium-catalyzed controlled carbopalladation of benzyne
Yoshikawa, Eiji,Radhakrishnan,Yamamoto, Yoshinori
, p. 7280 - 7286 (2007/10/03)
2-Trimethylsilylphenyl trifluoromethanesulfonate 1a, a benzyne precursor, reacted with the allylic chlorides 2a - f in the presence of CsF (2.0 equiv) and Pd2(dba)3·CHCl3 (2.5 mol %)-dppf (5 mol %) in a 1:1 mixed solvent of CH3CN and THF to produce the phenanthrene derivatives 3 along with their minor regioisomers 4 in good yields (i) and the reaction of 1a with 2a and the internal alkynes 15a,c - e afforded the naphthalene derivatives 16 in moderate yields (ii). The reaction of benzyne precursor 1a with the alkynes 15a - c,f - h in the presence of Pd(OAc)2 (5 mol %)-(o-tolyl)3P (5 mol %) catalyst and CsF (2.0 equiv) in CH3CN gave the phenanthrene derivatives 17 (iii), whereas the reaction of 1a with the alkynes 15a,b,i in the presence of the same catalysts and CsF in CH3CN - toluene gave the indene derivatives 18 in good yields (iv). Detailed mechanistic investigation revealed that the former two reactions i and ii proceed through carbopalladation to free benzyne, while the latter two reactions iii and iv proceed through the nonfree benzyne mechanism, in which the initial step of the catalytic cycle begins with Pd(0) insertion to the Ar - OTf bond of 1.
