Cu-Catalyzed cis-selective ring-opening cross-coupling of an oxabicyclic olefin with an organoboron reagent

The Cu(i)-catalyzed ring-opening cross-coupling of an oxabicyclic olefin with an organoboron reagent provides access to cis-2-aryl-1,2-dihydronaphthalen-1-ol derivatives, in contrast to the exclusive trans-selectivity in related Cu-catalyzed reactions with Grignard reagents. DFT calculations suggest that the reaction possibly proceeds via boronic ester by-product assisted ring-opening as an alternative pathway to the canonical beta-oxygen elimination as the rate-determining step.

Automated summary

The Cu(i)-catalyzed ring-opening cross-coupling of an oxabicyclic olefin with an organoboron reagent leads to the formation of cis-2-aryl-1,2-dihydronaphthalen-1-ol derivatives, differing from the trans-selectivity observed in similar Cu-catalyzed reactions with Grignard reagents. DFT calculations indicate a possible alternative pathway involving boronic ester by-product assisted ring-opening, instead of the canonical beta-oxygen elimination, as the rate-determining step.