Palladium-Catalyzed C–C Bond Formations via Activation of Carboxylic Acids and Their Derivatives

  • Applications of carboxylic acids and their derivatives in transition metal-catalyzed cross-coupling reactions regio-selectively forming Csp3-Csp2, and Csp2-Csp2 bonds were explored in this thesis. Several important organic building blocks such as aryl acetates, diaryl acetates, imines, ketones, biaryls, styrenes and polysubstituted alkenes were successfully accessed from carboxylic acids and their derivatives by the means of C–H activation and decarboxylative cross-couplings. An efficient and practical protocol for the synthesis of biologically important ethyl 2-arylacates through the dealkoxycarbonlative cross-coupling reaction between aryl halides and malonates was developed. Activation of the alpha-proton of alkyl esters by a copper catalyst allowed the deprotonation of esters even in the presence of mild bases, leading to a straightforward and efficient approach to alkyl alpha-diarylacetate from simple alkyl acetates and aryl halides. The addition of a primary amine into the coupling reaction of alpha-oxocarboxylic acids and aryl halides led to an unprecedented low-temperature redox-neutral decarboxylative coupling process, providing a green and efficient method for the preparation of azomethines, in which all the three substituents can be independently varied. A minor modification of this protocol allowed us to easily access the corresponding ketones. The decarboxylative coupling of robust aryl mesylates as well as polysubstituted alkenyl mesylates using our customized imidazolyl phosphine ligands was realized, further expanding the scope of carbon electrophiles in decarboxylative coupling reactions. Variation of the ligands led to two complementary protocols, providing the corresponding biaryls and polysubstituted olefins in high yields. The use of a new class of pyrimidinyl phosphine ligands dramatically reduced the reaction temperatures of decarboxylative cross-coupling reactions between aromatic carboxylic acids and aryl or alkenyl triflates. The new catalyst system for the first time allowed the efficient decarboxylative biaryls synthesis at only 100 °C, representing a significant achievement in redox-neutral decarboxylative coupling reactions.

Volltext Dateien herunterladen

Metadaten exportieren

Verfasserangaben:Bingrui Song
URN (Permalink):urn:nbn:de:hbz:386-kluedo-34878
Betreuer:Lukas J. Gooßen
Sprache der Veröffentlichung:Englisch
Veröffentlichungsdatum (online):16.04.2013
Jahr der Veröffentlichung:2013
Veröffentlichende Institution:Technische Universität Kaiserslautern
Titel verleihende Institution:Technische Universität Kaiserslautern
Datum der Annahme der Abschlussarbeit:09.04.2013
Datum der Publikation (Server):17.04.2013
Seitenzahl:XVI, 293
Fachbereiche / Organisatorische Einheiten:Fachbereich Chemie
DDC-Sachgruppen:5 Naturwissenschaften und Mathematik / 540 Chemie
Lizenz (Deutsch):Standard gemäß KLUEDO-Leitlinien vom 10.09.2012