Highly Selective Manganese(I)/Lewis Acid Cocatalyzed Direct C−H Propargylation Using Bromoallenes

A manganese(I)/Lewis acid cocatalyzed direct C−H propargylation with high selectivity has been developed. BPh3 was discovered to not only promote the reactivity, but also enhance the selectivity. Secondary, tertiary, and even quaternary carbon centers at the propargylic position could be directly constructed. Both internal and terminal alkynes are easily accessible. The chirality was successfully transferred from an axially chiral allene to central chirality. The reactivity of the manganese catalyst in this reaction was found to be unique among transition metal catalysts. Proper(gylation)! In a highly selective manganese(I)/Lewis acid cocatalyzed direct C−H propargylation, BPh3 not only promotes the reactivity, but also enhances the selectivity. Secondary, tertiary, and even quaternary carbon centers at the propargylic position could be directly constructed. The reactivity of the manganese catalyst in this reaction is unique among transition‐metal catalysts.