Asymmetric Total Synthesis and Absolute Configuration Determination of (−)-Verrupyrroloindoline

The first asymmetric total synthesis of (−)-verrupyrroloindoline (20% overall yield in 6 steps) is described. The short approach was enabled by Buchwald’s Cu­(II)-catalyzed asymmetric conjugate reduction, DMDO-triggered one-pot four-step tandem reaction, and the first amide-selective Ir-catalyzed direct reduction of β-carboethoxy tertiary lactam. Along with the total synthesis, the absolute configuration of natural verrupyrroloindoline was determined as 7<i>R</i>,10<i>R</i>,11<i>R</i>