Titanium Salalen Catalyzed Enantioselective Benzylic Hydroxylation

Abstract

The titanium complex of the cis‐1,2‐diaminocyclohexane (cis‐DACH) derived Berkessel‐salalen ligand is a highly efficient and enantioselective catalyst for the asymmetric epoxidation of terminal olefins with hydrogen peroxide (“Berkessel‐Katsuki catalyst”). We herein report that this epoxidation catalyst also effects the highly enantioselective hydroxylation of benzylic C−H bonds with hydrogen peroxide. Mechanism‐based ligand optimization identified a novel nitro‐salalen Ti‐catalyst of the highest efficiency ever reported for asymmetric catalytic benzylic hydroxylation, with enantioselectivities of up to 98 % ee, while overoxidation to ketone is marginal. The novel nitro‐salalen Ti‐catalyst also shows enhanced epoxidation efficiency, as evidenced by e.g. the conversion of 1‐decene to its epoxide in 90 % yield with 94 % ee, at a catalyst loading of 0.1 mol‐% only.

Aggregation-Driven Photoinduced α-C(sp3)–H Bond Hydroxylation/C(sp3)–C(sp3) Coupling of Boron Dipyrromethene Dye in Water Reported by Near-Infrared Emission

“…We demonstrate that the SB-CS state itself, rather than the commonly occurring mediating triplet-state, ,, initiates redox chemistry involving ROS, leading to α-C­(sp 3 )–H bond hydroxylation followed by heterodimerization via C sp 3 –C sp 3 coupling. Almost any source of visible light, including ambient sunlight, can be used to carry out this challenging class of reactions on the BODIPY scaffold, which are otherwise only possible using metal-containing catalysts and strong oxidants. ,,− Finally, the progress of photoproduction was tracked by monitoring the NIR signal resulting from the selective self-assembly of the terminal photoproduct 2-OH .…”