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Stereospecific Pd(0)-Catalyzed Arylation of an Allylic Hydroxy Phosphonate Derivative:  Formal Synthesis of (S)-(+)-ar-Turmerone

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journal contribution
posted on 28.11.2003, 00:00 by Bradley J. Rowe, Christopher D. Spilling
Reaction of the (1S)-allylic hydroxy phosphonate 1(S) with methyl chloroformate in pyridine yields the corresponding carbonate 3(S). The carbonate 3(S) undergoes a palladium-catalyzed arylation with p-tolyl tributylstannane to give both the 1E and 1Z vinyl phosphonates 6 (85:15). The E and Z vinyl phosphonates 6 were shown to have the opposite configuration at C-3. The major vinyl phosphonate isomer (3S,1E), was converted to (3S)-3-(p-tolyl)-butanal 8(S), completing a formal total synthesis of (S)-ar-turmerone 5a.