Synthesis of ynones by palladium-catalyzed acylation of terminal alkynes with acid chlorides.
Phosphane-free oxime-derived palladacycle 2 is an efficient precatalyst for the copper-free acylation of terminal alkynes with different carboxylic acid chlorides in toluene in the presence of 3 equiv of TEA as base, giving the corresponding ynones in good yields. The coupling reaction can normally be performed under air or under inert atmosphere when very low catalyst loadings (10(-3) mol % Pd) (turnover numbers (TONs) up to 23,000, turnover frequencies (TOFs) up to 958 h(-1)) or sensitive carboxylic acid chlorides are used. In addition, Pd(OAc)(2) has been shown as an efficient catalyst for the ligandless process, although usually working under higher loading conditions. This new protocol allows one to perform the synthesis of ynones at 110 degrees C, at room temperature, or under microwave irradiation conditions.
Departamento de Química Orgánica and Instituto de Síntesis Orgánica, Facultad de Ciencias, Universidad de Alicante, Apartado 99, E-03080 Alicante, Spain.
Diego A
DA
Alonso
Carmen
C
Nájera
M Carmen
MC
Pacheco