927-68-4Relevant articles and documents
Second-coordination sphere effects on the reactivities of Hoveyda-Grubbs-type catalysts: A ligand exchange study using phenolic moiety-functionalized ligands
Akiyama, Naoki,Goshima, Kenta,Hirota, Shun,Jatmika, Catur,Matsuo, Takashi,Wakabayashi, Kazumo
supporting information, p. 11618 - 11627 (2020/09/09)
The Hoveyda-Grubbs (HG) second-generation catalyst (HG-II), a Ru complex with a 2-isopropoxybenzylidene ligand, is extensively used for olefin metathesis, the rearrangement of carbon-carbon double bonds. A well-known strategy to control its complex reactivity is to modify the phenyl ring in the ligand, thereby directly influencing the coordination of the phenolic oxygen to the metal center. We, herein, report that a functional group attached to the phenolic moiety in the 2-alkoxybenzylidene ligand can indirectly affect the reactivities of HG-type complexes. In this work, the ligand exchange reactions between HG-II and phenolic moiety-modified 2-alkoxybenzylidene ligands are useful for evaluating the structural effects of the ligands. Specifically, an ethylene amide or an ester group at the terminal phenolic moiety in the benzylidene ligand was found to influence the relative stabilities of HG-type complexes compared to that of the HG-II complex. The structural analyses proved that the observed effects of the functional groups on the complex stabilities originate from the interactions with a chlorido ligand in HG-type complexes without changes in coordination fashions at the metal centers. It was found that the outer-sphere interactions also influence the catalytic activities of HG-type complexes, namely, the properties of HG-type complexes can be controlled by outer-sphere structural factors toward the metal center (i.e., "the second-coordination sphere effect"). In the design of functionalized HG-type complexes, the outer-sphere structural effects need to be considered in addition to the optimization of the metal coordination site.
Isopropenyl acetate: A cheap and general acylating agent of alcohols under metal-free conditions
Temperini, Andrea,Minuti, Lucio,Morini, Tommaso,Rosati, Ornelio,Piazzolla, Francesca
, p. 4051 - 4053 (2017/09/27)
Functionalized primary, secondary and tertiary alcohols are efficiently acetylated by isopropenyl acetate and catalytic p-TsOH.
Acetylcholine-like and trimethylglycine-like PTA (1,3,5-Triaza-7- phosphaadamantane) derivatives for the development of innovative Ru- and Pt-based therapeutic agents
Ferretti, Valeria,Fogagnolo, Marco,Marchi, Andrea,Marvelli, Lorenza,Sforza, Fabio,Bergamini, Paola
, p. 4881 - 4890 (2014/06/09)
The PTA N-alkyl derivatives (PTAC2H4OCOMe)X (1X: 1a, X = Br; 1b, X = I; 1c, X = PF6; 1d, X = BPh4), (PTACH 2COOEt)X (2X: 2a, X = Br; 2b, X = Cl; 2c, X = PF6), and (PTACH2CH2COOEt)X (3X: 3a, X = Br; 3c, X = PF 6), presenting all the functional groups of the natural cationic compounds acetylcholine or trimethylglycine combined with a P-donor site suitable for metal ion coordination, were prepared and characterized by NMR, ESI-MS, and elemental analysis. The X-ray crystal structures of 1d and 2c were determined. Ligands 1c, 2b, and 3c were coordinated to Pt(II) and Ru(II) to give the cationic complexes cis-[PtCl2(L)2]X2 and [RuCpCl(PPh3)(L)]X (L = 1, 2, 3, X = Cl or PF6) designed with a structure targeted for anticancer activity. The X-ray crystal structure of [CpRu(PPh3)(PTAC2H4OCOMe)Cl]PF6 (1cRu) was determined. The antiproliferative activity of the ligands and the complexes was evaluated on three human cancer cell lines.
