Catalytic Carbo- and Aminoboration of Alkenyl Carbonyl Compounds via Five- and Six-Membered Palladacycles

• Published in: Journal of the American Chemical Society Vol. 140; no. 9; pp. 3223 - 3227
• Main Authors: Liu, Zhen, Ni, Hui-Qi, Zeng, Tian, Engle, Keary M
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 07.03.2018; Amer Chemical Soc
• Subjects: Alkenes - chemical synthesis; Alkenes - chemistry; Amination; Borates - chemical synthesis; Borates - chemistry; Butyrates - chemical synthesis; Butyrates - chemistry; Carbon; carbonyl compounds; carboxylic acids; Catalysis; Chemistry; Chemistry, Multidisciplinary; Fatty Acids, Monounsaturated - chemical synthesis; Fatty Acids, Monounsaturated - chemistry; Lewis bases; nitrogen; palladium; Palladium - chemistry; Physical Sciences; Science & Technology; HALIDES; CROSS-COUPLING REACTIONS; BIS(PINACOLATO)DIBORON; SYNERGISTIC CATALYSIS; BONDS; ALKYL ELECTROPHILES; PALLADIUM CATALYSIS; UNACTIVATED TERMINAL ALKENES; ARYLBORATION; BORYLATION
• ISSN: 0002-7863; 1520-5126; 1520-5126
• DOI: 10.1021/jacs.8b00881

A palladium­(II)-catalyzed alkene difunctionalization reaction has been developed, wherein B2pin2 is used to trap chelation-stabilized alkylpalladium­(II) intermediates that are formed upon nucleopalladation. A range of carbon and nitrogen nucleophiles were found to be suitable coupling partners in this transformation, providing moderate to high yields. Both 3-butenoic and 4-pentenoic acid derivatives were reactive substrate classes, affording β,γ- and γ,δ-difunctionalized carboxylic acid derivatives. This work represents a new strategy to synthesize highly functionalized secondary boronates that complements existing methods.