Department of Chemistry, Gwangju Institute of Science and Technology, 123 Cheomdan-gwagi-ro, Buk-gu, Gwangju 61005, Republic of Korea.
J Org Chem. 2023 Jun 2;88(11):6878-6889. doi: 10.1021/acs.joc.3c00183. Epub 2023 May 2.
Organoazide rearrangement constitutes versatile synthetic strategies but typically requires an extremely strong acid and/or a high reaction temperature. Our group recently discovered the remarkable accelerating effect of the geminal fluorine substituent that enables the facile rearrangement of azides into imidoyl fluorides without the aid of acid under much milder reaction conditions. The role of geminal fluorine was elucidated by both experimental and computational investigations. This new reactivity led to the development of a practical one-step tandem preparative method for potentially useful and bench-stable imidoyl fluorides from a wide range of structurally diverse geminal chlorofluorides. Our additional efforts to expand the reaction scope regarding the migrating group, halogen, and carbonyl function are described, and the synthetic utility of the imidoyl fluoride products was demonstrated in hopes of promoting the use of this under-appreciated functional group in the synthetic organic community.
有机叠氮化物重排构成了多种通用的合成策略,但通常需要极其强的酸和/或高温。我们小组最近发现偕二氟取代基的显著加速效应,在温和得多的反应条件下,无需酸即可轻松将叠氮化物重排成异酰氟化物。通过实验和计算研究阐明了偕二氟的作用。这种新的反应性导致了一种实用的一步串联制备方法的发展,可从广泛的结构多样的偕二氯氟化物中得到潜在有用且稳定在实验台上的异酰氟化物。我们还努力扩大反应范围,包括迁移基团、卤素和羰基功能,描述了异酰氟化物产物的合成实用性,希望促进在合成有机界中使用这个未被充分认识的官能团。