Frustrated Lewis-Pair Neighbors at the Xanthene Framework: Epimerization at Phosphorus and Cooperative Formation of Macrocyclic Adduct Structures

Attachment of a pair of P-stereogenic mesityl(alkynyl)phosphanyl groups at the 4- and 5-positions of a 9,9-dimethylxanthene framework gave mixtures of the respective rac- and meso-bisphosphanyl diastereoisomers. They slowly epimerized in a thermally induced reaction with Gibbs activation barriers of about 25 kcal mol⁻¹ at room temperature (measured and DFT calculated). The reaction of the meso-mesityl(tert-butylethynyl)phosphanyl derivative with two molar equivalents of Piers′ borane [HB(C₆F₅)₂] led to the formation of the alkylidene-bridged geminal bisphosphane/borane-frustrated Lewis pair system. The compound was obtained enriched (>85 %) in the rac diastereoisomer. With a variety of bifunctional donor substrates, the rac-bis-P/B FLP formed macrocyclic compounds. They were all formally derived from meso-configurated diastereoisomers of the bisphosphanylxanthene backbone.