Frustrated Lewis Pair-Catalyzed Cycloisomerization of 1,5-Enynes via a 5-endo-dig Cyclization/Protodeborylation Sequence

The first frustrated Lewis pair‐catalyzed cycloisomerization of a series of 1,5‐enynes was developed. The reaction proceeds via the π‐activation of the alkyne and subsequent 5‐endo‐dig cyclization with the adjacent alkene. The presence of PPh3 was of utmost importance on the one hand to prevent side reactions (for example, 1,1‐carboboration) and on the other hand for the efficient protodeborylation to achieve the catalytic turnover. The mechanism is explained on the basis of quantum‐chemical calculations, which are in full agreement with the experimental observations. Cycloisomerization without a metal: The first FLP‐catalyzed C−C bond forming reaction is described as proceeding through a cycloisomerization/protodeborylation sequence. The reaction mechanism is supported by X‐ray crystal structure analysis of intermediates, kinetic experiments, and by quantum‐mechanical calculations.