Feedstock chemical dichloromethane as the C1 source for the chemoselective multicomponent synthesis of valuable 1,4,2-dioxazoles

Commun Chem. 2024 Nov 21;7(1):273. doi: 10.1038/s42004-024-01364-3.

Abstract

The development of mild and practical strategies to produce value-added fine chemicals directly from inexpensive and readily available commodity chemicals is actively pursued by chemists. However, the application of feedstock chemical dichloromethane (DCM) as the C1 source in organic synthesis is still in its infancy. Herein, we describe a multicomponent strategy for the chemoselective synthesis of valuable 1,4,2-dioxazoles by using DCM as a C1 source. Critical to the success of this process is tuning of the type of nucleophiles to inhibit the easily-occurring side reactions. This approach features mild and simple conditions, excellent chemoselectivity, metal free, and broad substrate scope covering different types of nucleophiles. Furthermore, its synthetic utility is further demonstrated by the preparation of deuterated 1,4,2-dioxazoles, the late-stage functionalization of complex molecules and large-scale synthesis. Preliminary mechanistic studies indicate the dual roles of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as both a proton scavenger and a nucleophilic catalyst. This work provides not only a platform for DCM application, but also an excellent complementary strategy to the established 1,4,2-dioxazoles synthesis.