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21.14.1.2.7.3 Variation 3: Cross-Coupling Reactions

DOI: 10.1055/sos-SD-021-00911

Whitehead, A.; Sieck, S. R.; Mukherjee, S.; Hanson, P. R.Science of Synthesis, (200521924.

Vinylphosphonates can be prepared via perfluoroalkylsulfonyl enol ethers from an array of acylphosphonates.[‌55‌] For example, acylphosphonates 63 can be treated with nonafluo­robutane-1-sulfonyl fluoride and a base in tetrahydrofuran to generate enolates 64 (Scheme 20); it was established that the use of 1,8-diazabicyclo[5.4.0]undec-7-ene at 45 ºC gives optimal yields. Subsequent palladium-catalyzed coupling reactions with acetylenes or vinylstannanes were performed to generate diethoxyphosphoryl-containing enynes, as well as dienes, e.g. 65, in good yields.[‌56‌]

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