Paroi Bidisha, Pegu Chayanika, Mane Manoj V, Patil Nitin T
Department of Chemistry, Indian Institute of Science Education and Research Bhopal, Bhopal Bypass Road, Bhauri, Bhopal-, 462 066, India.
Centre for Nano and Material Science, Jain (Deemed-to-be University), Jain Global Campus Kanakapura, Bangalore, Karnataka-, 562112, India.
Angew Chem Int Ed Engl. 2024 Aug 12;63(33):e202406936. doi: 10.1002/anie.202406936. Epub 2024 Jun 30.
Cope rearrangements have garnered significant attention owing to their ability to undergo structural reorganization in stereoselective manner. While substantial advances have been achieved over decades, these rearrangements remained applicable exclusively to parent 1,5-hexadienes. Herein, we disclose the gold-catalyzed arylative Cope rearrangement of 1,6-heptadienes via a cyclization-induced [3,3]-rearrangement employing ligand-enabled gold redox catalysis. Detailed mechanistic investigations including several control experiments, cross-over experiment, HRMS analysis, P NMR and DFT studies have been performed to underpin the mechanism.
由于其能够以立体选择性方式进行结构重排,科普重排受到了广泛关注。尽管几十年来已经取得了重大进展,但这些重排仅适用于母体1,5 - 己二烯。在此,我们报道了通过环化诱导的[3,3] - 重排,利用配体促进的金氧化还原催化实现的金催化1,6 - 庚二烯的芳基化科普重排。我们进行了详细的机理研究,包括多个对照实验、交叉实验、高分辨质谱分析、磷核磁共振和密度泛函理论研究,以支持该反应机理。