Palladium Catalyzed Oxidative Carbonylation

Organic chemistry is a chemistry subdiscipline involving the scientific study of the structure, properties, and reactions of organic compounds and organic materials. The construction of C-C, C-X bonds remains the core contents in organic chemistry. During the last decades, transition-metal catalyzed cross-couplings have been intensively investigated and become an important tool of organic chemist.On the other hand, as one of the important chemical industrial raw materials, CO has been widely applied in organic synthesis. In the 80s of last century, the concept of C1 chemistry has been put forward which injects new vitality into CO chemical industry. Since the pioneering works of Prof. Heck which applied CO into cross-coupling, the transition-metal catalyzed carbonylation has attracted more and more attentions and become a hot research topic. Oxidative C-H carbonylation, the incorporation of CO into an organic molecule C-H bonds, is now widely recognized as a very important and potential tool in industrial and organic chemistry, which meets the requirement of "atom economy", "green chemistry". It allows the direct synthesis of important carbonyl compounds starting from the simplest C-1 unit.The thesis firstly reviewed the history of development of carbonylation, and the Pd-catalyzed C-H oxidative carbonylation is also introduced in detail. The research work of this thesis is focused on the palladium catalyzed oxidative carbonylation for the synthesis of 3-methyleneindolin-2-ones, a,?-unsaturated amides, benzo[cd]indol-2(1H)-ones, phenanthridin-6(5H)-ones and a,?-unsaturated ketones by rational design. It mainly consists of the following parts:1. The first palladium/copper-catalyzed aerobic oxidative C-H alkenylation/N-dealkylative carbonylation of tertiary anilines has been developed. Various functional groups were tolerated and acrylic ester could also be suitable substrates. This transformation provided an efficient and straightforward protocol for the synthesis of biologically active 3-methyleneindolin-2-one derivatives from cheap and simple substrates. Preliminary mechanism studies were conducted indicating the possible route of this transformation.2. A novel Pd/Cu-catalyzed chemoselective aerobic oxidative N-dealkylation/ carbonylation reaction has been developed. Tertiary amines are utilized as a "reservoir" of "active" secondary amines in this transformation, which inhibits the formation of undesired by-products and the deactivation of the catalysts. This protocol allows for an efficient and straightforward construction of synthetically useful and bioactive (E)-?,?-unsaturated amide derivatives from easily available tertiary amines, olefins and CO.3. Pd-catalyzed selective amine-oriented C8-H bond functionalization/N-dealkylative carbonylation of naphthyl amines has been achieved. The amine group from dealkylation is proposed to be the directing goup to promote this process. It represents a straightforward and easy method to various benzo[cd]indol-2(1H)-one derivatives. Moreover, O2 is utilized as the terminal oxidant to promote the oxidative carbonylation process. Preliminary mechanism studies are conducted indicating the possible route of this transformation.4. A straightforward method to various phenanthridin-6(5H)-ones has been achieved through Pd/Cu-catalyzed aerobic oxidative C-H bond activation/N-dealkylative carbonylation of tertiary [1,1'-biphenyl]-2-amines. A wide range of functional groups are tolerated as well. Moreover, O2 is utilized as the terminal oxidant to promote the oxidative carbonylation process.5. As an important category of oxidative cross-couplings, the Pd-catalyzed C-H carbonylation which introduces CO into the organic molecules has become a hot research topic. However it remains a great challenge to achieve the chemo-selectivity in Pd-catalyzed oxidative carbonylation between two C-H bonds. Herein we have developed the selective Pd-catalyzed dual C-H carbonylation of pyrroles with olefins to obtain the chalcone derivatives, which avoid the by-products of homo-coupling, alkenylation of pyrroles. This protocol might make a contribution to the various Pd-catalyzed dual C-H carbonylation.