Bond energy enabled amine distinguishing strategy: chemo-, regioselective 1, 3-diamination of (trifluoromethyl)alkenes with different amines by two C(sp3)–F bond cleavages. Issue 5 (2nd February 2022)

• Record Type: Journal Article
• Authors: Zeng, Hao; Li, Hengyuan; Li, Chengxi; Jiang, Huanfeng; Zhu, Chuanle
• Is Part Of: Organic chemistry frontiers. Volume 9:Issue 5(2022)
• Page Start: 1383
• Page End: 1388
• Publication Date: 2022-02-02
• Subjects: Chemistry, Organic -- Periodicals; 547.005
• DOI: 10.1039/d1qo01849c
• Languages: English
• ISSNs: 2052-4110

Abstract

Abstract : ipso -Defluorinative amination-triggered 1, 3-diamination of (trifluoromethyl)alkenes with different amines affords various monofluoroalkenylated acyclic 1, 3-diamines in high yields with excellent Z / E selectivity. Abstract : The methods to distinguish between amines are rarely investigated. In this article, a bond energy enabled amine distinguishing strategy is reported. With (trifluoromethyl)alkenes as linchpins, a chemo-, regioselective three-component defluorinative 1, 3-diamination reaction with two different amine nucleophiles was achieved. Remarkably, the different bond energies of the two sequentially cleaved C(sp 3 )–F bonds efficiently distinguishes the two different amines via their different priorities involved in these two different steps. Thus, this ipso -defluorinative amination-triggered 1, 3-diamination transformation affords various monofluoroalkenylated acyclic 1, 3-diamines in high yields with excellent Z / E selectivity. This protocol is successfully applied in the late-stage functionalization of drug derivatives from Celebrex and Sulthiame. A sequential ipso -/γ-selective defluorinative amination pathway is involved via two C(sp 3 )–F bond cleavages in a CF3 group.