Chiral N,P-ligands' Application In Asymmetric Allylation And Suzuki Coupling Reaction

Transition-metal-catalyzed reaction has the extremely widespread application in organic synthesis.The reaction was applied successfully in the construction of various functional compounds,such as C-H,C-C,C-N,C-O,C-S,and other carbon-heteroatoms bond-forming approaches,which can synthesize a variety of complex active pharmaceutical intermediates and chiral organic molecules.The design and synthesis of the novel multifunctional phosphine ligands is one of the most important topics in transition-metal-catalyzed reaction.In this thesis,we have synthesized a series of D-camphor-based chiral N,P-ligands,and studied the application of these ligands in Allylic alkylation reaction and Suzuki cross-coupling reaction.Here we report a modularly synthetic strategy to D-camphor-based chiral N,P-ligands on the basis of previous findings in Schiff base and chiral ligand chemistry.Commercially available D-camphor is extremely attractive for the development of effective phosphine ligands because of multiple stereogenic centers on the camphor backbone and the rigid structure as well as the reactive ketone moiety.The chiral N,P-ligands were easily synthesized and stabilized in the air.Finally,the effectiveness of this new Schiff base with chirality matching as a bidentate chelating N,P-ligand is demonstrated in the palladium-catalyzed allylic alkylation and Suzuki cross-coupling reaction.The research shows that,a family of new Schiff base derived from chiral D-camphor has been determined as an effective phosphine ligand for the asymmetric palladium-catalysed allylic alkylation of indole,in which the corresponding products with various functional groups were achieved in good yields(92%)and excellent enantioselectivities(up to 98% ee).The chiral N,P-ligands catalyze Suzuki cross-coupling reaction of bulky aryl-bromides,in which the corresponding product was achieved in excellent yield(97%).D-camphor-derived Schiff base revealed the privileged role in the palladium catalysis.