We summarize in this review the recent development of chiral phosphoric acid (CPA)-catalyzed asymmetric dearomatization reactions.

A 1,2-reductive dearomatization of quinolines and copper­(II) acetate monohydrate/(R,R)-Ph-BPE/P­(p-tolyl)3-catalyzed enantioselective hydroamination sequence was developed, affording diverse 4-amino-1,2,3,4-tetrahydroquinolines with high levels of enantioselectivity in either a stepwise or one-pot fashion. Pleasingly, internal cis-cyclic alkenes, which are challenging substrates in copper hydride-catalyzed enantioselective hydroamination reactions, were transformed efficiently under mild conditions.

A copper(II) acetate/(R)‐DTBM‐SEGPHOS‐catalyzed ring opening of benzofurans and enantioselective hydroamination cascade with dimethoxymethylsilane (DMMS) and hydroxylamine esters is described. Starting from readily available substituted benzofurans, a series of chiral N,N‐dibenzylaminophenols, which are of high interest in pharmaceutical chemistry, were obtained with excellent enantioselectivities (up to 66 % yield, 94 % ee).