Aryl phosphonates are an important class of molecules with applications as pharmaceuticals, agrochemicals, flame retardants, and organic electronics. We have been developing a procedure for preparing novel aryl phosphonates that are structurally complex and functionally dense. This procedure relies on the sequential formation of two strained aromatic intermediates. The first intermediate is formed by treating an electrophilic aryl iodide with a hindered Grignard reagent. The resulting electrophile reacts with an O-silyl phosphite or phosphine oxide to simultaneously form C-Si and C-P bonds. Treating the resulting product with fluoride anion gives rise to the second intermediate, which is capable of reacting with a number of nucleophiles and pi-systems. The starting material is prepared in only two steps from resorcinol (and analogues thereof), and the reagents required for generating each of the intermediates are inexpensive. We have used this protocol to prepare a variety of ortho and meta substituted aryl phosphonates with numerous functional groups. This presentation will discuss our efforts related to discovery and optimization of reaction conditions. Additionally, we will discuss the scope of amenable arenes, O-silyl phosphorous(III) reactants, and nucleophiles.

Synthesis of structurally complex aryl phosphonates

2019 Spring National Meeting

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