Transition Metal Catalysis in Fluorous Media: Practical Application of a New Immobilization Principle to Rhodium-Catalyzed Hydroborations of Alkenes and Alkynes

Abstract

Addition of a yellow-orange toluene solution of [Rh(Cl)(COD)]2 to a colorless CF3C6F11 solution of P(CH2CH2Rf6)3 (Rf6 = (CF2)5CF3)3) gives a colorless toluene solution of COD and an orange CF3C6F11 solution of ClRh[P(CH2CH2Rf6)3]3 (1). Evaporation of CF3C6F11 gives analytically pure 1 (94%), which is insoluble in most organic solvents and stable to 300 °C. Alkenes, catecholborane, and CF3C6F11 solutions of 1 (950:950:1 mol ratio for norbornene) are stirred for 1−24 h at 40 °C (heterogeneous conditions). The resulting alkylboranes are extracted with benzene (2×; turnover number (TON) 854 (90%) for norbornene), toluene, or THF, and the catalyst solution is reused (TON 2409 for three cycles). Subsequent reactions with H2O2/NaOH give alcohols, which are isolated in 92−77% yields (11 examples). Longer reaction times afford TON values higher than 10 000 (<0.1 mol % 1). Analogous reactions of alkynes yield alkenylboranes (89−88%). Pinacolborane additions are also catalyzed. A higher homologue of 1, ClRh[P(CH2CH2...