1, 3‐Sulfinate Migration Triggered by α‐Imino Carbene and Divergent Zwitterion Cyclization: Synthesis of Cyclopropane, Dihydropyrrole, and Azepane Ring Systems. Issue 8 (1st February 2023)

• Record Type: Journal Article
• Authors: Xu, Huaping; Kong, Xiaoyu; Cen, Mengjie; Xu, Ze‐Feng; Duan, Shengguo; Li, Chuan‐Ying
• Is Part Of: European journal of organic chemistry. Volume 26:Issue 8(2023)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2023-02-01
• Subjects: carbenes -- cyclization -- divergent synthesis -- triazoles -- zwitterions; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1002/ejoc.202201417
• Languages: English
• ISSNs: 1434-193X

Abstract

Abstract: Cyclopropane, dihydropyrrole, and azepane ring systems were synthesized conveniently from sulfinate‐tethered triazoles. The divergent synthetic strategy started with the unique 1, 3‐sulfinate migration of an α‐imino carbene. The efficient reaction allowed control of the zwitterion bearing multiple reactive sites depending on the increased stability of the resulting carbocation and anion. The sulfinate was converted to a sulfone after the group migration, and a stable anion bearing two electron‐withdrawing groups was thus formed. Catalytic amounts of iodide acted as a switch for the synthesis of cyclopropanes and dihydropyrroles. The reaction merits including readily available substrates, mild reaction conditions, and excellent functional group compatibility qualified this protocol a possible synthetic tool for cyclic compounds, especially for N‐heterocycles. Abstract : Three birds with one stone: A convenient divergent synthetic strategy was established by regulation on the intramolecular annulation modes of zwitterion bearing multiple reactive sites, yielding various functionalized 3‐, 5‐, and 7‐membered rings.