Forming Benzylic Iodides via a Nickel Catalyzed Diastereoselective Dearomative Carboiodination Reaction of Indoles. Issue 15 (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 international edition. Volume 58:Issue 15(2019)
• Page Start: 5095
• Page End: 5099
• Publication Date: 2019-03-12
• Subjects: carbohalogenation -- dearomative reaction -- diastereoselective catalysis -- indoles -- nickel; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201900659
• Languages: English
• ISSNs: 1433-7851

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. Abstract : A diastereoselective dearomative carboiodination reaction is reported. Utilizing the unique reactivity of nickel, the carboiodination reaction was expanded to non‐activated aromatic double bonds to form a previously unattainable class of iodides. Furthermore, a broadly applicable method to avoid the use of a metallic reducing agent by utilizing an alkyl phosphite as the ligand is reported.