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[摘要]:(Organometallic and Organometalloidal Compounds) Section Stereoselective enolization of a,b-unsatd. aldehydes RCH:CHCHO by tBuOK/N-methylpyrrolidone (NMP) followed by phosphorylation by phosphorochloridate ClP(O)(OEt)2 gave (E)-dienol phosphates in good yields and stereoselectivities. Reaction of RR1CHCR2:CR3CHO with ClP(O)(OEt)2 and tBuOK/NMP in THF gave (1E)-RR1C:CR2CR3:CHOP(O)(OEt)2 with 80-97% yields and >99% stereoselectivities. The formation of C3-C4-double bond is less stereoselective, and up to 24% of (3Z)-isomers were obtained. The prepd. dienyl phosphates can be coupled with Grignard reagents in the presence of iron salts, giving terminal dienes and trienes. |
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