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The synthesis of five hydroxycinnamoyl amides (HCAs) was accomplished and their identification and quantification in the green coffee bean samples of  Coffea   arabica ,  Coffea   canephora , and  Coffea   liberica  was performed. The HCAs  p -coumaroyl- N -tyrosine  1b , caffeoyl- N -phenylalanine  2b , caffeoyl- N -tyrosine  3b , and  p -coumaroyl- N -tryptophan  4b  were characteristic of the  C. canephora  species while caffeoyl- N -tryptophan  5b  was present in both  C. canephora  and  C. arabica , but with higher content in  C. canephora . The HCAs presence was also analyzed in  C. liberica  for the first time and none of the targeted compounds was found, indicating that this species is very similar to  C. arabica  species. Between  C. canephora  samples from various origins, significant differences were observed regarding the presence of all the HCAs, with  C. canephora  from Tanzania containing all five derivatives.

Hydroxycinnamoyl Amino Acids Conjugates: A Chiral Pool to Distinguish Commercially Exploited Coffea spp.