Pyrroloindolines are widely present in natural products. In this review, we summarize state-of-the-art of catalytic asymmetric synthesis of pyrroloindolines, as well as related applications to natural products total synthesis.

A sequential phosphine‐catalyzed asymmetric [3+2] annulation of aldimines with allenoates and oxidative central‐to‐axial chirality transfer strategy has been developed. This approach is operationally simple, allowing for rapid access to a range of axially chiral CF3‐containing 2‐arylpyrroles with high enantiomeric excess. Furthermore, an atroposelective synthesis of esaxerenone is presented, illustrating the practical potential of the reported method.

We introduced a type of allenic ketone as a dielectrophilic C4 synthon in phosphine-mediated reactions. The high electrophilicity of the advanced intermediates created upon phosphine activation empowered the utilization of 3,3′-bisoxindoles as a two-carbon reaction partner in a highly enantioselective [4 + 2] annulation, allowing for facile creation of spirocyclic bisindoline structures containing two contiguous quaternary stereogenic centers. Synthetic manipulations of the [4 + 2] annulation product led to concise total synthesis of (−)-folicanthine.

The asymmetric allylic alkylation (AAA) of achiral Morita−Baylis−Hillman (MBH) carbonates with 3,3′-bisindolines under the catalysis of amino-acid-derived bifunctional phosphines was accomplished. With the AAA approach introduced herein, challenging 3,3′-bisindolines bearing an all-carbon quaternary stereocenter (C3a) have been constructed in good yields with good to excellent enantioselectivties. In addition, the synthetic value of this protocol was demonstrated by the facile synthesis of the core skeleton of gliocladin C.

No abstract