Reakcje addycji, cykloaddycji i sprzęgania w syntezie nowych pochodnych arenów i heteroarenów z podstawnikami bitienylowymi

Dissertation is devoted to the synthesis of 1,2,3-triazoles, N-substituted pyrroles and various arenes (such as: anthracene, phenanthrene, pyrene) derivatives, all containing up to four 2,2’-bithiophen-5-yl groups. The first group of compounds, ie. pyrrole derivatives were obtained by CuCl catalyzed addition reaction of commercially available primary amines (eg. aniline, methyl 4-aminobenzoate, N-ethyl-3-aminocarbazole) and 1,4-bis(2,2'-bithiophen-5-yl)-buta-1,3-diyne. Optimal conditions for developed synthesis and the isolation procedure for obtained products (ie. trisubstituted pyrroles) were determined. The impact of microwave radiation and catalyst fragmentation on the course and yield of the hydroamination reactions were examined too. Moreover, a developed methodology of synthesis and isolation (on a scale of few grams) of butadiyne derivative, became the subject of a patent for an invention titled "A process for preparing 1,4-bis(2,2’-bithiophen-5-yl)buta-1,3-diyne". Derivatives of 1,2,3-triazole were obtained by the cycloaddition reaction of the organic azides (eg. decyl, 2,4-difluorbenzyle, 2,2’-bithienyl) and terminal (5-ethynyl-2,2'-bithiophene) or internal alkynes (1,2-bis(2,2’-bithiophen-5-yl)acetylene) catalyzed with copper and ruthenium compounds respectively. The third group of compounds obtained under the doctoral dissertation were arenes (eg. benzene, fluorene, anthracene) and heteroarenes (eg. carbazole) derivatives containing up to four 2,2'-bithiophen-5-yl groups in the molecule, attached to the aromatic core by a triple bond. These derivatives were obtained by Sonogashira coupling reactions catalyzed with [Pd]/Cu in the presence of an amine. Also primary electrochemical (redox potentials, stability of the obtained polymers under the oxidation-reduction conditions) and spectroscopic (absorption, emission, quantum yield, etc.) properties of the selected compounds ware determined and the obtained results were compared with the values designated theoretically with methods of quantum mechanics

Synthesis of unsymmetrical alkyl acetals via addition of primary alcohols to allyl ethers mediated by ruthenium complexes

Ru-catalyzed synthesis of mixed alkyl–alkyl acetals via addition of primary alcohols to allyl ethers has been extended to include long-chain and/or functionalized substrates. The catalytic systems for these reactions were generated from RuCl2(PPh3)3 and [RuCl2(1,5-COD)]x and phosphines [PPh3 or P(p-chlorophenyl)3] or SbPh3 . Of particular importance is the almost quantitative elimination of transacetalization. The addition proceeds through allyl complexes, not via isomerization of allyl ethers––subsequent addition of ROH to vinyl ethers

Multifaceted Strategy for the Synthesis of Diverse 2,2'-Bithiophene Derivatives

New catalytically or high pressure activated reactions and routes, including coupling, double bond migration in allylic systems, and various types of cycloaddition and dihydroamination have been used for the synthesis of novel bithiophene derivatives. Thanks to the abovementioned reactions and routes combined with non-catalytic ones, new acetylene, butadiyne, isoxazole, 1,2,3-triazole, pyrrole, benzene, and fluoranthene derivatives with one, two or six bithiophenyl moieties have been obtained. Basic sources of crucial substrates which include bithiophene motif for catalytic reactions were 2,2'-bithiophene, gaseous acetylene and 1,3-butadiyne

Multifaceted Strategy for the Synthesis of Diverse 2,2'-Bithiophene Derivatives

New catalytically or high pressure activated reactions and routes, including coupling, double bond migration in allylic systems, and various types of cycloaddition and dihydroamination have been used for the synthesis of novel bithiophene derivatives. Thanks to the abovementioned reactions and routes combined with non-catalytic ones, new acetylene, butadiyne, isoxazole, 1,2,3-triazole, pyrrole, benzene, and fluoranthene derivatives with one, two or six bithiophenyl moieties have been obtained. Basic sources of crucial substrates which include bithiophene motif for catalytic reactions were 2,2'-bithiophene, gaseous acetylene and 1,3-butadiyne