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

Abstract

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.

Keywords: 1,5-enynes; cycloisomerization; frustrated Lewis pairs; kinetic isotope effect; protodeborylation.