Science of Synthesis

Whitehead, A.; Sieck, S. R.; Mukherjee, S.; Hanson, P. R., Science of Synthesis, (2005) 21, 925.

When dialkyl benzoylphosphonates react with trialkyl phosphites a carbene intermediate is formed via anionic intermediates.[‌57‌] Thus, dimethyl 2-phenoxybenzoylphosphonate (‌66‌) reacts with trimethyl phosphite to facilitate the formation of a carbene intermediate (‌Scheme 21‌). Initially the carbene inserts into the π-system of the aromatic ring to generate ‌67‌. Subsequent rearrangement produces tricyclic ‌68‌ as the major product in a mixture of ‌68‌, ‌69‌, and ‌70‌. Similarly, it was demonstrated that this process works for carbene insertion into nonaromatic substituents.[‌58‌]

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