Aryl phosphonates represent an important class of compounds with broad application in medicinal chemistry, materials science, and agricultural chemistry. We have found that silyl-containing aryl phosphonates can be prepared in good yield by reaction between silyl phosphites and bis(sulfonyl) analogues of 2-halophenols and resorcinols. The reaction proceeds quickly and gives silylated products in good yields. Furthermore, the resulting silylated product also readily transformed into a variety of unreported aryl phosphonates via known dipolar cycloaddition reactions. Namely, treating the silylated product with fluoride induces E2 elimination of the silyl and sulfonyl groups to form a strained pi system, which spontaneously engages a 1,3-dipole. This presentation will describe the discovery and optimization of the silyl-containing aryl phosphonate synthesis methodology. Additionally, amenable 1,3-dipolar cycloaddition reactions will be presented. Computational studies will also be presented, which provided numerous insights into the mechanism of reaction along with the source of cycloaddition regioselectivity.

Two-step synthesis of complex aryl phosphonates via sequential elimination and 1,3-dipolar cycloaddition

255th National Meeting (2018)

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