New organic transformations based on electrophilic and superelectrophilic activation in strong acids
by Paknia, Farzaneh, Ph.D., UNIVERSITY OF SOUTHERN CALIFORNIA, 2008, 219 pages; 3329412

Abstract:

This dissertation covers the development of new methodologies based on Friedel-Crafts alkylation, acylation and hydroxyalkylation through electrophilic or superelectrophilic activation using boron trifluoride monohydrate and polymer supported superacids for the synthesis of fluorinated and heterocyclic compounds.

Chapter 1 briefly reviews the history of superelectrophiles and their chemistry. Superelectrophilic chemistry has made a significant contribution in Friedel-Crafts and related electrophilic reactions.

Chapter 2 deals with the triflic acid catalyzed Friedel-Crafts alkylation reaction of trifluoromethylated acrylic acid with arenes for the synthesis of biologically important trifluoromethylated dihydrocoumarins, indanones and arylpropanoic acids.

Chapter 3 explores the application of BF3-H2O as an efficient acid catalyst as well as a solvent for Friedel-Crafts hydroxyalkylation reaction of trifluoromethylated and difluoromethylated hemiacetals with aromatics for the synthesis of trifluoroethylated and difluoroethylated aromatic building blocks.

Chapter 4 describes the application of BF3-H2O as a substitute to trifluoromethanesulfonic acid for hydroxyalkylation reaction of pyridinecarboxaldehydes with aromatics through superelectrophilic protosolvation. Preparation of various biologically important diarylmethylpyridine derivatives has been discussed.

Chapter 5 encompasses the preparation of poly(4-vinylpyridinium) poly(triflic acid) as a polymer supported (immobilized) solid equivalent of triflic acid. (PVP-TfOH) has been applied as a convenient and efficient solid superacid catalyst for Friedel-Crafts hydroxyalkylation and acylation reactions of arenes through superelectrophilic activation.

Chapter 6 demonstrates a convenient protocol for the synthesis of medicinally important 1,5-benzodiazepine and perimidine derivatives in presence of boron trifluoride monohydrate (BF3-H2O) as an efficient and convenient acid catalyst.

Chapter 7 examines the synthesis of the hydrocinnamamide derivatives through triflic acid catalyzed Friedel-Crafts reaction of α,β-unsaturated amides with aromatic compounds through superelectrophilic activation.

 
AdviserSurya Prakash
SchoolUNIVERSITY OF SOUTHERN CALIFORNIA
SourceDAI/B 69-09, p. , Dec 2008
Source TypeDissertation
SubjectsOrganic chemistry
Publication Number3329412
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