Asymmetric Conjugate Addition of Organoboron Reagents to Common Enones Using Copper Catalysts

Copper
complexes of phosphoramidites efficiently catalyzed asymmetric
addition of arylboron reagents to acyclic enones. Importantly, rare
1,4-insertion of arylcopper­(I) was identified which led directly to
O-bound copper enolates. The new mechanism is fundamentally different
from classical oxidative addition/reductive elimination of organocopper­(I)
on enones.

磷酰胺基铜络合物有效地催化了芳基硼试剂对环状烯酮的不对称加成反应。值得注意的是，罕见的1,4-插入反应被鉴定，该反应直接导致铜氧键合的烯醇化物形成。新的反应机理与经典的有机铜（I）在烯酮上的氧化加成/还原消除反应有着根本的不同。