Bio-based synthesis of secondary arylamines from (−)-shikimic acid

A specific family of secondary arylamines, including diarylamines and arylalkylamines have been synthesized in good yields starting from the renewable and biomass-based feedstock (−)-shikimic acid (1). The tandem cross-coupling and aromatization reactions between primary amines and the intermediate (−)-methyl-3-dehydroshikimate (3) are crucial for realizing this strategy. The application of arylamines and alkylamines provided 3-arylamino-4-hydroxybenzoates (5) and 3,4-dihydroxy-5-alkylaminobenzoates (7) respectively via a selective dehydration or dehydrogenation process.