Solvent‐Controlled Enantiodivergent Construction of P(V)‐Stereogenic Molecules via Palladium‐Catalyzed Annulation of Prochiral N‐Aryl Phosphonamides with Aromatic Iodides

• Published in: Angewandte Chemie International Edition Vol. 63; no. 41; pp. e202409366 - n/a
• Main Authors: Tian, Qingyu, Ge, Jin, Liu, Yaopeng, Wu, Xi, Li, Zhenghao, Cheng, Guolin
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 07.10.2024
• Edition: International ed. in English
• Subjects: Cascade chemical reactions; Catellani reaction; Chemical reactions; enantiodivergent reaction; Enantiomers; enantioselectivity; Iodides; P-stereogenic compound; Palladium; Solvents; P-stereogenic compound n; palladium; Enantioselectivity; enantiodivergent reaction; Catellani reaction
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202409366

In this work, we describe an efficient and modular method for enantiodivergent accessing P(V)‐stereogenic molecules by utilizing the catalytic atroposelective Catellani‐type C−H arylation/desymmetric intramolecular N‐arylation cascade reaction. The enantioselectivity of this protocol was proved to be tuned by the polarity of the solvent, thus providing a wide range of both chiral P(V)‐stereogenic enantiomers in moderate to good yields with good to excellent enantiomeric excesses. Noteworthy is that the strategy developed herein represents an unprecedented example of solvent‐dictated inversion of the enantioselectivity of P(V)‐stereogenic compounds. A new strategy for enantiodivergent accessing P(V)‐stereogenic molecules via palladium/norbornene cooperative catalysis was established. The enantioselectivity of this protocol was tuned by the polarity of the solvent, thus providing both enantiomers of the P(V)‐stereogenic molecules using a single chiral norbornene catalyst.