Mechanism and Origin of the Stereoselectivity in the Palladium-Catalyzed trans Hydroboration of Internal 1,3-Enynes with an Azaborine-Based Phosphine Ligand.Chemistry. 2018 Jan 02; 24(1):178-186.C
An azaborine-based phosphine-Pd catalyst was introduced by the Liu group to promote trans hydroboration of the C≡C triple bond of internal 1,3-enyne substrates. Despite the excellent yield and selectivity observed experimentally, the mechanism and the origin of this special trans selectivity remained unknown. Herein, a comprehensive theoretical investigation was performed to clarify these issues. Accordingly, two main mechanisms (inner- and outer-sphere) were proposed and examined. Different from the conventional inner-sphere mechanism, in which the transition metal is involved in H-B bond cleavage, this reaction follows an outer-sphere mechanism, in which Pd does not directly participate in H-B bond cleavage. More specifically, the favorable pathway followed a Tsuji-Trost type reaction, in which the H-B bond was weakened by the formation of a four-coordinate boron intermediate (i.e., the boron is attached to the terminal carbon of the alkyne group). It then underwent a hydride-transfer process with the assistance of a second borane molecule, and finally reductive elimination generated the trans hydroboration product. Further analysis ascribed the origin of the special trans selectivity to the unique steric effect and electronic effect introduced by the special κ1 -P-η2 -BC coordination pattern.
