Acetate-catalyzed hydroboration of CO2 for the selective formation of methanol-equivalent products

The present study details the use of the acetate anion, an inexpensive and robust anion, as a CO2 hydroboration catalyst for the selective formation, in most cases, of methanol-equivalent borane products. Thus, upon heating (90 degrees C, PhBr), tetrabutylammonium, sodium and potassium acetate (1, 2 and 3, respectively) effectively catalyze CO2 hydroboration by pinacolborane (pinB-H) to afford CO2 reduction products HOCOBpin (A), pinBOCH(2)OBpin (B) and methoxyborane (C). In most cases, high selectivity for product C with higher borane loading and longer reaction time with a TON of up to 970 was observed. The reduction catalysis remains efficient at low catalyst loading (down to 0.1 mol%) and may also be performed under solvent-free conditions using salt 1 as a catalyst, reflecting the excellent robustness and stability of the acetate anion. In control experiments, a 1/1 1/pinB-H mixture was found to react fast with CO2 at room temperature to produce formate species [pinB(O2CH)(OAc)][N(Bu-n)(4)] (5) through CO2 insertion into the B-H bond. DFT calculations were also performed to gain insight into the acetate-mediated CO2 hydroboration catalysis, which further supported the crucial role of acetate as a Lewis base in CO2 functionalization catalysis by pinB-H. The DFT-estimated mechanism is in line with experimental data and rationalizes the formation of the most thermodynamically stable reduction product C through acetate catalysis.