Abstract
2-(Propa-1,2-dienyl)-, 2-(buta-1,2-dienyl)-, and 2-(3-methylbuta-1,2-dienyl)-substituted 5,5-dimethyl-1,3,2-dioxaphosphinane 2-oxides 1a-c react readily upon heating with thiols under catalyst-free, base-free, and solvent-free conditions to give sulfanyl-substituted phosphonates. The reaction undergoes to essential completion within 15 minutes under microwave radiation. While 1a ,b react with 4-chlorothiophenol to afford both 2-[2-(4-chlorophenylsulfanyl)prop-1-enyl]- 12 and 2-[2-(4-chlorophenylsulfanyl)prop-2-enyl]-5,5-dimethyl-1,3,2-dioxaphosphinane 2-oxides 13 , 1c gives 2-[2-(4-chlorophenylsulfanyl)-3-methylbut-2-enyl]-5,5-dimethyl-1,3,2-dioxaphosphinane 2-oxide (13d ) regioselectively. Molecular oxygen undergoes a novel reaction with the allene 1c to give propargylic alcohol 2-(3-hydroxy-3-methylbut-1-ynyl)-5,5-dimethyl-1,3,2-dioxaphosphinane 2-oxide (16 ) via the corresponding hydroperoxide; the structures of these were confirmed by X-ray crystallography. The synthetic utility of the sulfanyl-substituted allyphosphonate 13d in the Horner-Wadsworth-Emmons reaction to afford synthetically valuable sulfanyl-substituted buta-1,3-dienes and a conjugated triene is demonstrated.
Key words
allenes - thiol addition - oxygenation - Horner-Wadsworth-Emmons reaction - allenylphosphonates
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