For the first time, using PCl3, a range of tert-butyl esters is chlorinated successfully, allowing access of both aromatic acid chlorides and aliphatic acid chlorides in good yields. The method features simple reaction conditions and wide substrate scope. Various tert-butyl esters including aryl esters, alkenyl esters, and alkyl esters were tolerated well in the reaction. A plausible mechanism is proposed.

C14H8Br2N4O6⋅2(C2H6OS), triclinic, P 1 ‾ $P\bar{1}$ (no. 2), a = 6.1463(12) Å, b = 8.3637(16) Å, c = 12.461(3) Å, α = 85.578(5)°, β = 85.942(5)°, γ = 86.310(5)°, V = 635.9(2) Å3, Z = 1, R gt (F) = 0.0601, wR ref (F 2) = 0.0983, T = 296 K. CCDC no.: 2057510