Forming Benzylic Iodides via a Nickel Catalyzed Diastereoselective Dearomative Carboiodination Reaction of Indoles. (12th March 2019)

• Record Type: Journal Article
• Authors: Marchese, Austin D.; Lind, Florian; Mahon, Áine E.; Yoon, Hyung; Lautens, Mark
• Is Part Of: Angewandte Chemie. Volume 131:Number 15(2019)
• Page Start: 5149
• Page End: 5153
• Publication Date: 2019-03-12
• Subjects: Carbohalogenierung -- Dearomatisierung -- Diastereoselektive Katalyse -- Indole -- Nickel; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201900659
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: A diastereoselective dearomative carboiodination reaction is reported. We report a novel metal‐catalyzed approach to install reactive secondary benzylic iodides. Utilizing the unique reactivity of nickel, we have expanded the carboiodination reaction to non‐activated aromatic double bonds forming a previously unattainable class of iodides. We also report a broadly applicable method to avoid the use of a metallic reducing agent by utilizing an alkyl phosphite as the ligand. The reaction is thought to proceed through a syn intramolecular carbonickelation across a 2‐substituted indole followed by a diastereoretentive reductive elimination of the carbon−iodine bond. The complex iodinated indolines generated in the reaction were obtained in moderate to good yields and good to excellent diastereoselectivity. The products were easily functionalized by a variety of synthetic methods.