Brønsted Acid Catalyzed Phosphoramidic Acid Additions to Alkenes: Diastereo- and Enantioselective Halogenative Cyclizations for the Synthesis of C- and P‑Chiral Phosphoramidates

• Published in: Journal of the American Chemical Society Vol. 136; no. 42; pp. 14734 - 14737
• Main Authors: Toda, Yasunori, Pink, Maren, Johnston, Jeffrey N
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 22.10.2014; Amer Chemical Soc
• Subjects: Acids - chemistry; Alkenes - chemistry; Amides - chemical synthesis; Amides - chemistry; Catalysis; Chemistry; Chemistry Techniques, Synthetic; Chemistry, Multidisciplinary; Communication; Cyclization; Phosphoric Acids - chemical synthesis; Phosphoric Acids - chemistry; Physical Sciences; Science & Technology; Stereoisomerism; Substrate Specificity; BROMOLACTONIZATION; REARRANGEMENT; DIARYLPHOSPHINES; ACTIVATION; ASYMMETRIC-SYNTHESIS; RESOLUTION; HIGHLY EFFICIENT SYNTHESIS; PHOSPHINE OXIDES; IODOLACTONIZATION; DERIVATIVES
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja5088584

The first highly diastereo- and enantioselective additions of a halogen and phosphoramidic acid to unactivated alkenes have been developed, catalyzed by a chiral Brønsted acid. A unique feature of these additions is the opportunity for stereocontrol at two noncontiguous chiral centers, carbon and phosphorus, leading to cyclic P-chiral phosphoramidates. In addition to their inherent value, the phosphoramidates are precursors to enantioenriched epoxy allylamines.