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: Faculty of Chemistry and Pharmacy

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.

• Item Type: Theses (Dissertation, LMU Munich)
• Keywords: Copper, Zinc, Heteroaromatics, Aminals, Amines
• Subjects: 500 Natural sciences and mathematics; 500 Natural sciences and mathematics > 540 Chemistry and allied sciences
• Faculties: Faculty of Chemistry and Pharmacy
• Language: English
• Date of oral examination: 4. October 2011
• 1. Referee: Knochel, Paul
• Signature of the printed copy: 0001/UMC 19793