Formation of macrocyclic ring systems by carbonylation of trifunctional p/b/b frustrated lewis pairs

Abstract

The trifunctional P/B/B frustrated Lewis pairs 11a-c featuring bulky aryl groups at phosphorus [Dmesp (a), Tipp (b), Mes∗ (c)] react with H2 by heterolytic hydrogen splitting followed by cleavage of HB(C6F5)2 to give the zwitterionic six-membered heterocyclic PH phosphonium/borate products 14a-c. Compounds 11a,b react with carbon monoxide by means of a Lewis acid induced CO insertion/rearrangement sequence that eventually results in the formation of the macrocyclic dimers 17a,b. The respective carbonylation reaction of the Mes∗P/B/B FLP gives the macrocyclic trimer 18c. The new products were characterized spectroscopically and by X-ray diffraction and the reaction mechanism was analyzed by DFT calculations.