Metal-free C(sp3)–H functionalization of sulfonamidesviastrain-release rearrangement
Open Access
- 22 January 2021
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Chemical Science
- Vol. 12 (11), 4034-4040
- https://doi.org/10.1039/d0sc06603f
Abstract
With the increasing awareness of sustainable chemistry principles, the development of an efficient and mild strategy for C(sp3)–H bond activation of nitrogen-containing compounds without the utilization of any oxidant and metal is still highly desired and challenging. Herein, we present a metal-free reaction system that enables C–H bond functionalization of aliphatic sulfonamides using DABCO as a promoter under mild conditions, affording a series of α,β-unsaturated imines in good yields with high selectivities. This protocol tolerates a broad range of functionalities and can serve as a powerful synthetic tool for the late-stage modification of complex compounds. More importantly, control experiments and detailed DFT calculations suggest that this process involves [2 + 2] cyclization/ring-cleavage reorganization, which opens up a new platform for the establishment of other related reorganization reactions.Funding Information
- National Natural Science Foundation of China (21901114)
- Natural Science Foundation of Jiangsu Province (BK20180685)
- Jiangsu Provincial Department of Education (18KJB150017)
- Nanjing Tech University (38274017102, 39837101)
- Jiangsu National Synergistic Innovation Center for Advanced Materials
This publication has 67 references indexed in Scilit:
- Copper-Catalyzed Regioselective Intramolecular Oxidative α-Functionalization of Tertiary Amines: An Efficient Synthesis of Dihydro-1,3-OxazinesAngewandte Chemie, 2013
- Discovery of a Metalloenzyme-like Cooperative Catalytic System of Metal Nanoclusters and Catechol Derivatives for the Aerobic Oxidation of AminesJournal of the American Chemical Society, 2012
- A Biologically Inspired CuI/Topaquinone‐Like Co‐Catalytic System for the Highly Atom‐Economical Aerobic Oxidation of Primary Amines to IminesAngewandte Chemie, 2012
- Visible‐Light‐Induced Selective Photocatalytic Aerobic Oxidation of Amines into Imines on TiO2Chemistry – A European Journal, 2012
- Ruthenium-Catalyzed Cascade N- and C(3)-Dialkylation of Cyclic Amines with Alcohols Involving Hydrogen Autotransfer ProcessesAdvanced Synthesis & Catalysis, 2010
- Small molecule antagonists for chemokine CCR3 receptorsMedicinal Research Reviews, 2010
- Enantioselective Biocatalytic Oxidative Desymmetrization of Substituted PyrrolidinesAngewandte Chemie, 2010
- Selective Functionalization of sp3 C−H Bonds Adjacent to Nitrogen Using (Diacetoxyiodo)benzene (DIB)The Journal of Organic Chemistry, 2009
- Aza-Mannich Condensation of Sulfinimine Promoted by Tetrabutylammonium Fluoride: Synthesis of α,β-Unsaturated SulfinimineSynlett, 2006
- Total Synthesis of the Unusual Marine Alkaloid (-)-Papuamine Utilizing a Novel Imino Ene ReactionJournal of the American Chemical Society, 1995