Transition metal-catalyzed synthesis of nitrogen-containing compounds

• Main Author: Liu, Yu
• Other Authors: School of Physical and Mathematical Sciences
• Format: Theses and Dissertations
• Language: English
• Published: 2013
• Subjects: DRNTU::Science::Chemistry::Organic chemistry::Organic synthesis
• Online Access: http://hdl.handle.net/10356/51346
• Institution: Nanyang Technological University

This thesis describes transition metal-catalyzed synthesis of nitrogen-containing compounds, including two parts. In Part I, we have demonstrated an efficient palladium(II)-catalyzed oxidative Heck cross-coupling protocol which allows the synthesis of highly substituted enamides that are important synthetic intermediates with a broad utility in various applications, and also achieved the transformation of enamide to the corresponding β-amino acid derivative under the asymmetric hydrogenation conditions with high ee value and high yield. In Part II, we developed an efficient and practical rhodium(III)-catalyzed intramolecular annulation of alkyne tethered hydroxamates for the synthesis of 3-hydroxyalkyl isoquinolones and 6-hydroxyalkyl-2-pyridones. This reaction features high reverse-regioselectivity, broad substrate scope, excellent functional group tolerance, and mild reaction conditions at low catalyst loading, and in particular use an internal oxidant strategy (using N-O as oxidizing directing group). Furthermore, a convenient total synthesis of (±) antofine, (±) septicine and (±) tylophorine and construction of rosettacin, involving Rh(III)-catalyzed C-H bond functionalization of alkyne tethered hydroxamates as the key step, was accomplished.