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Four undescribed oxylipin vanillyl acetals with four stereogenic carbons were separated through the natural herbs of Solanum lyratum. A thorough set of spectroscopic methods were utilized to elucidate the structures and relative designs of 1-4. The absolute configurations associated with the naturally occurring substances tend to be assigned as 7S, 9'S, 10'S, 11'R during the web site of six-membered cyclic acetal ac