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Phosphinoferrocene conjugates of selected amino acids
Tauchman, Jiří ; Štěpnička, Petr (advisor) ; Růžička, Aleš (referee) ; Dvořák, Dalimil (referee)
A series of chiral phosphinoferrocene amides was prepared by the condensation either of 1'- (diphenylphosphino)ferrocene-1-carboxylic acid (Hdpf) or its planar-chiral 1,2-isomers and amino acid methyl esters in the presence of peptide coupling agents. The resulting phosphinoamides were tested as ligands in Cu-catalyzed asymmetric conjugate additions of diethylzinc to chalcones and in Pd-mediated asymmetric allylic substitution reactions of 1,3- diphenylallyl acetate with the respective nucleophile (alkylation, amination and etherification). The catalytic tests were focused on an optimization of the reaction parameters (solvent, temperature, base, metal/ligand ratio) and on survey of various substrates. Compounds based on Hdpf proved to be better ligands in both catalytic reactions than their planar chiral analogues. In order to rationalize the influence of the ligand structure on the reaction course and also to interpret the catalytic results, several model complexes were prepared and structurally characterized. Other three series of non-chiral complexes were prepared from the corresponding (η6 - arene)ruthenium(II) precursor and Hdpf-glycine conjugates; the neutral complexes of the type [(arene)RuCl2(Hdpf-Gly(R)-κP)] (arene = benzene, p-cymene, hexamethyl-benzene; R = OMe, NH2, OH) as well as two...
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Phosphinoferrocene amides and hydrazides
Solařová, Hana ; Štěpnička, Petr (advisor) ; Kubíček, Vojtěch (referee)
Title: Phosphinoferrocene amides and hydrazides Author: Hana Solařová Department: Department of Inorganic Chemistry Supervisor: doc. RNDr. Petr Štěpnička, Ph.D. Abstract: While studying functionalized phosphinoferrocene ligands, we recently turned to phosphinoferrocene carboxamides. These donors already proved to be versatile ligands for coordination chemistry and catalysis. This led us to synthesize and study the archetypal representative, 1'-(diphenylphosphino)-1-carbamoylferrocene (5), and the corresponding hydrazide 6. PPh2 COOH Fe Hdpf PPh2 CONH2 Fe 5 PPh2 CONHNH2 Fe 6 This work describes the preparation of primary amide 5 and hydrazide 6 from 1'- (diphenylphosphino)-1-ferrocenecarboxylic acid (Hdpf) via the corresponding acylbenzo- triazole derivative. The hydrazide was alternatively obtained from Hdpf methylester and hydrazine hydrate. Both newly synthesized compounds were characterized by spectroscopic methods (NMR, IR, and MS) and elemental analysis, and their crystal structures were determined by single-crystal X-ray crystallography. The amide was further utilized in the preparation of several palladium complexes, which were characterized in a similar manner including X-ray crystallography. One palladium complex was obtained also from the hydrazide. However, the hydrazide was used mainly as a...
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