Intramolecular Nozaki–Hiyama–Kishi reactions and Ln(III)-catalyzed allylic rearrangement as the key steps towards 10-membered ring enediynes

A general and facile synthesis of the 3-substituted 10-membered ring enediynes 18–22 from the aldehydes 8 and 15 has been established by utilizing the intramolecular Nozaki–Hiyama–Kishi reaction and the lanthanide(III)-catalyzed rearrangement of allylic alkoxyacetates as the key steps. This work provides ready access to the (E)-3-acyloxy-4-(arylmethylidene)cyclodeca-1,5-diynes, which can be converted into the bioactive enediynes under physiological conditions.