Manganese(I)-Catalyzed Substitutive C-H Allylation.

The first manganese(I)-catalyzed C-H allylations with ample scope were achieved by carboxylate assistance. The highly selective C-H/C-O functionalizations proved viable with densely substituted allyl carbonates, and the organometallic C-H allylation strategy set the stage for expedient late-stage diversification with excellent levels of positional selectivity.