Syntheses and Reactions of Allylic and Homoallylic Pyrophosphate Tetraesters

Abstract Pyrophosphate tetraesters possessing allylic and homoallylic side chains were synthesized. Reaction of alkyl allyl (and 3-methyl-3-butenyl) phosphorochloridates with sodium hydrogencarbonate gave P1,P2-dialkyl P1,P2-diallyl [and P1,P2-bis(3-methyl-3-butenyl)] pyrophosphates. Condensation of alkyl allyl (and 3-methyl-3-butenyl) phosphorochloridates with dialkyl phosphates gave trialkyl allyl (and 3-methyl-3-butenyl) pyrophosphates. Reactions of crotyl (2-butenyl) pyrophosphates with various nucleophiles such as phenolic ethers, aromatic amines, and nitrogen-containing heterocycles in the presence of boron trifluoride etherate gave good to moderate yields of crotylated products. The crotyl pyrophosphates were found to be much more reactive than the corresponding orthophosphate esters.