Application Of The Radical Reaction And Palladium-Catalyzed Cross-Coupling Reaction For The C-C/C-P Bond Formation

In this thesis, transition metal catalyzed C-C or C-P bond-forming reactions are studied. The main results obtained are shown as belows:1. A novel silver-catalyzed carbophosphonation reaction of a,a-diaryl allylic alcohols with H-phosphonates was achieved via the addition of P-radicals, and sequentially undergo 1,2-migration of an aryl group. A series of y-ketophosphonates with different substituents were readily obtained (Scheme 1). In the case of substrates with different aryl groups, selective migration was observed. The carbonphosphonation of alkenes has been demonstrated to serve as an ideal entry to β-aryl-y-ketophosphonates.2. The palladium-catalyzed C-H phosphonation of coumarins and H-phosphonates was performed. The phosphonation selectively accured at the C-3 position of coumarins, affording the corresponding products in moderate to good yields (Scheme 2). The methodology provides a new, efficient, atom-economy protocol for the efficient preparation of 3-phosphonated coumarins.3. A palladium complex based on N,N-dimethylethanolamine was synthesized via ligand exchange at room temperature (Cat. I). The catalyst activity was investigated as follows:(1) The complex was used in the Sonogashira cross-coupling reaction of aryl iodides, β-bromostyrene with terminal alkynes in the absence of CuX co-catalyst and any ligand at room temperature, affording the corresponding products in moderate to excellent yields. It was found that (Z)-β-bromostyrene reacts with terminal alkynes with retention of the steric configuration.(2) The complex catalyzed Suzuki cross-coupling reaction of aryl bromides was developed. A series of substituted biphenyls were obtained under mild reaction conditions in moderate to excellent yields. Aryl chlorides containing electron-withdrawing groups also gave the corresponding products in good yields.(3) The Oxdative-Heck cross-coupling reaction of arylboronic acids with olefins was described. With the complex as catalyst, a series of substituted alkenes were obtained in moderate to excellent yields. This protocol could be tolerated to arylboronic acids containing electron-donating or electron-withdrawing groups and a wide range of olefins such as acrylate, allyl esters, allyl ethers and alkenylphosphonate. R1=H,OH,Me,tBu,OMe,Cl,Br,COMe,CF3 25 examples R2=H,Me up to 98% yield R3=ester, alkyl,aryl Scheme 6...