Pd-Catalyzed Suzuki-Miyaura Coupling Of Allylic Carbonates With Arylboronic Acids

Since Suzuki-Miyaura coupling reaction was explored by Suzuki and Miyaura in 1979, it has been considered by scientists as a powerful method for C-C bond formation and successfully used for industry. Over the past thirty years, a broad range of electrophiles undergoing cross-couplings with organoboronic acids, including alkyl, aryl, alkenyl, and alkynyl groups have been widely reported. However, the coupling reaction with allylic derivatives has been rarely reported, and most of the reports, the allylic partners have been confined to primary allylic halides or alcohol derivatives. The coupling reaction of unsymmetric 1,3-disubstituted secondary allylic derivatives with arylboronic acids could afford the allylic partners with chiral carbon atoms, in addition, there are a lot of significant natural compounds which all contain this kind of coupling framework, but it is rarely reported. So it makes great sense of exploring a highly efficient and selective method for the coupling reaction of unsymmetric 1,3-disubstituted secondary allylic derivatives with arylboronic acids In my thesis,we represent the first general method for Pd-catalyzed Suzuki?Miyaura coupling reaction of unsymmetric 1,3-disubstituted secondary allylic carbonates with arylboronic acids. The Pd-catalyzed reaction has been developed in the wet solvent under base free system to afford allyl?aryl coupling products in high level of isolated yields with complete regio- and E/Z selectivities with good to excellent chemoselectivities. The reaction reveals wide generality and is suitable for the cross-coupling of various unsymmetric 1,3-disubstituted secondary allylic carbonates with arylboronic acids. The stereochemical course of the coupling reaction has been demonstrated that are excellent chirality transfer with inversion of the stereochemistry, and the coupling reaction was successfully applied to the synthesis of (S)-Naproxen.Our studies effectively extend the scope of Suzuki?Miyaura coupling reaction and provide a simple, convenient and practical protocol for allyl?aryl coupling.