Biomimetic Total Syntheses of (+)-Dihydrolyfoline and (−)-5-epi-Dihydrolyfoline

The first asymmetric total syntheses of (+)-dihydrolyfoline and (−)-5-epi-dihydrolyfoline have been achieved in five and six steps with 4.6% and 14% overall yields, respectively, in which the chiral biaryl axes were constructed in a highly regioselective and stereoselective manner via a biogenetic enzymatic oxidative couplings of phenols, and the requisite quinolizidinone cores were prepared by an enzymatic Mannich reaction.