Synthesis of Axially Chiral CF -Substituted 2-Arylpyrroles by Sequential Phosphine-Catalyzed Asymmetric [3+2] Annulation and Oxidative Central-to-Axial Chirality Transfer.

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 CF -containing 2-arylpyrroles with high enantiomeric excess. Furthermore, an atroposelective synthesis of esaxerenone is presented, illustrating the practical potential of the reported method.

Catalytic asymmetric preparation of pyrroloindolines: strategies and applications to total synthesis.

Pyrroloindolines are important and privileged polycyclic indoline motifs that are widely present in natural products and bio-significant molecules. From an organic chemistry perspective, their rigid tricyclic molecular architectures with a fully substituted carbon center at the C3a-position pose a great challenge to synthetic chemists. In a biological context, pyrroloindoline-containing alkaloids display a plethora of promising activities, making them significant in biological sciences and drug development.

Phosphine-Catalyzed Asymmetric Allylic Alkylation of Achiral MBH Carbonates with 3,3'-Bisindolines: Enantioselective Construction of Quaternary Stereogenic Centers.

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.