Oxidative Copper(I)-Mediated Cycloamination. Preparation and Reactions of Heteroaromatic Benzylic Zinc Compounds. Novel Preparation of Tertiary Benzylic and Phenethylic Amines

Wagner, Andreas Johannes (2011): Oxidative Copper(I)-Mediated Cycloamination. Preparation and Reactions of Heteroaromatic Benzylic Zinc Compounds. Novel Preparation of Tertiary Benzylic and Phenethylic Amines. Dissertation, LMU München: Fakultät für Chemie und Pharmazie

Abstract

1. It was demonstrated that the two-fold deprotonation of benzofuran-3-yl- and benzothiophen-3-ylanilines using nBuLi, followed by transmetalation using CuCl·2LiCl afforded cyclic amidocuprates which were readily oxidized using 2,3,5,6-tetrachlorobenzo-p-quinone (“chloranil”) to furnish new tetracyclic benzofuro- and benzothieno[2,3-b]indoles. 2. A method was developed, starting from heteroaryl organometallics, for the synthesis of non-conjugated heteroaromatic benzylic zinc compounds which could be reacted with a wide range of electrophiles. 3. The preparation of mixed aminals from Mannich’s cation and a range of metal amides was performed and their subsequent ionization to (methylene)iminium ions using trifluoroacetic anhydride was achieved. Trapping of these iminium ions with a range of organometallic substrates in a one-pot fashion led to the efficient formation of sterically hindered tertiary benzylic and phenethylic amines.

• Dokumententyp: Dissertationen (Dissertation, LMU München)
• Keywords: Copper, Zinc, Heteroaromatics, Aminals, Amines
• Themengebiete: 500 Naturwissenschaften und Mathematik ; 500 Naturwissenschaften und Mathematik > 540 Chemie
• Fakultäten: Fakultät für Chemie und Pharmazie
• Sprache der Hochschulschrift: Englisch
• Datum der mündlichen Prüfung: 4. Oktober 2011
• 1. Bericht­erstatter:in: Knochel, Paul