Regiocontrolled synthesis of cis-enediynes via intramolecular trapping of allytic cations

Article abstract of DOI:10.1016/S0040-4039(98)01834-6

Trapping of allylic cations possessing 1,2-dialkynyl groups by an external nucleophile such as ROH yields cis-enediynes in a regioselective manner; while similar allylic cations react with an internal nucleophilic group to afford exclusively cis-enediynes. This regiocontrolled allylic rearrangement has been used successfully in the synthesis of a number of 2,5- dihydro-2-benzofuryl cis-enediynes 5 and the sulfur analogs.