2876-03-1Relevant articles and documents
Enantioselective Kinetic Resolution/Desymmetrization of Para-Quinols: A Case Study in Boronic-Acid-Directed Phosphoric Acid Catalysis
Huang, Banruo,He, Ying,Levin, Mark D.,Coelho, Jaime A. S.,Bergman, Robert G.,Toste, F. Dean
supporting information, p. 295 - 301 (2019/11/03)
A chiral phosphoric acid-catalyzed kinetic resolution and desymmetrization of para-quinols operating via oxa-Michael addition was developed and subsequently subjected to mechanistic study. Good to excellent s-factors/enantioselectivities were obtained over a broad range of substrates. Kinetic studies were performed, and DFT studies favor a hydrogen bonding activation mode. The mechanistic studies provide insights to previously reported chiral anion phase transfer reactions involving chiral phosphate catalysts in combination with boronic acids. (Figure presented.).
Tunable arylative cyclization of 1,6-enynes triggered by rhodium(III)-catalyzed C-H activation
Fukui, Yuki,Liu, Ping,Liu, Qiang,He, Zhi-Tao,Wu, Nuo-Yi,Tian, Ping,Lin, Guo-Qiang
supporting information, p. 15607 - 15614 (2014/12/11)
Two tunable arylative cyclizations of cyclohexadienone-containing 1,6-enynes are reported via rhodium(III)-catalyzed C-H activation of O-substituted N-hydroxybenzamides. The use of different O substituents, i.e. O-Piv and O-Me, on the directing group allows the formation of either tetracyclic isoquinolones through an N-Michael addition process or hydrobenzofurans through a C-Michael addition process. Mechanistic investigations of these two cascade reactions clearly indicated that the C-H bond cleavage process was involved in the turnover-limiting step. Furthermore, the cyclization products could be subjected to various transformations for elaborating the pharmaceutically and synthetically valuable potential. This is the first example of a rhodium(III)-catalyzed arylative cyclization reaction of 1,6-enynes, and the results extend the application realm of CpRhIII-catalyzed C-H activation cascade reactions.