Enantioselective Formation of All-Carbon Quaternary Centers via C-H Functionalizatioh of Methanol: Iridium-Catalyzed Diene Hydrohydroxymethylation

摘要

The first catalytic enantioselective C-C couplings of methanol (＞30 × 10~6 tons/year) are reported. Insertion of 2-substituted dienes into the methanol C-H bond occurs in a regioselective manner to form all-carbon quaternary centers with excellent levels of enantioselectiv-ity using an iridium-PhanePhos catalyst. Mechanistic studies corroborate a Curtin-Hammett scenario in which methanol dehydrogenation triggers rapid, reversible diene hydrometalation en route to regioisomeric allyliridium-formaldehyde pairs, yet single constitutional isomers are formed.