Anthocyanin Biosynthesis – https://www.kegg.jp/kegg-bin/highlight_pathway?scale=1.0&map=map00942&keyword=flavonoids Anthocyanidins (aglycones) and anthocyanins (glycosides) are common plant pigments and belong to a structural subclass of flavonoids characterized by a 2- phenylbenzopyrylium unit. They are derived along the flavonoid modification pathways and further separated into three types, pelargonidin, cyanidin, and delphinidin, due to the different number of hydroxyl groups in the phenyl group. (Flavonoid Biosynthesis) -> [1,2,3] 1) Pelargonidin -> anthocyanidin 3-O-glucosyltransferase -> Pelargonidin 3-O- glucoside -> [1,2,3,4,5,6,7] 1) anthocyanin 3-O-glucoside-6’’-O- malonyltransferase -> Pelargonidin 3-O-(6-O-malonyl-beta-D-glucoside) -> anthocyanidin 3-O-glucoside-3’’,6’’-O-dimalonyltransferase -> Pelargonidin 3-O-3’’,6’’-O-dimalonylglucoside OR 2) anthocyanidin 3-O-glucoside 2’’-O- glucosyltransferase -> Pelargonidin 3-O-sophoroside OR 3) Pelargonidin 3- O-rutinoside -> cyanidin 3-O-rutinoside 5-O-glucosyltransferase -> Pelargonidin 3-O-rutinoside 5-O-beta-D-glucoside OR 4) cyanidin 3-O- glucoside 7-O-glucosyltransferase (acyl-glucose) -> Pelargonidin 3,7-di-O- beta-D-glucoside OR 5) anthocyanidin 3-O-glucoside 2’’’-O- xylosyltransferase -> Pelargonidin 3-O-beta-D-sambubioside -> anthocyanin 3-O-sambubioside 5-O-glucosyltransferase -> Pelargonidin 5-O-beta-D- glucoside 3-O-beta-D-sambubioside OR 6) anthocyanidin 3-O-glucoside 6’’-O- acyltransferase -> Pelargonidin 3-(6-p-coumaroyl)glucoside &/OR Pelargonidin 3-O-(6-caffeoyl-beta-D-glucoside) -> Pelargonidin 3-O-(6- caffeoyl-btea-D-glucoside) 5-O-beta-D-glucoside -> anthocyanin 5-O- glucoside-6’’’-O-malonyltransferase -> 4’’’-Demalonylsalvianin -> anthocyanin 5-O-glucoside-4’’’-O-malonlytransferase -> Salvianin OR 7) anthocyanidin 3-O-glucoside 5-O-glucosyltransferase / caynidin 3-O- glucoside 5-O-glucosyltransferase (acyl-glucose) -> Pelargonin -> [1,2] 1) anthocyanidin 3-O-glucoside 6’’-O-acyltransferase -> Pelargonidin 3-O-(6- caffeoyl-btea-D-glucoside) 5-O-beta-D-glucoside -> anthocyanin 5-O- glucoside-6’’’-O-malonyltransferase -> 4’’’-Demalonylsalvianin -> anthocyanin 5-O-glucoside-4’’’-O-malonlytransferase -> Salvianin OR 2) anthocyanin 5-aromatic acyltransferase -> [1,2] 1) Pelargonidin 3-O-beta- D-glucoside 5-O-(6-coumaroyl-beta-D-glucoside) OR 2) Pelargonidin 3- glucoside 5-caffeoylglucoside 2) Cyanidin -> [1,2] 1) anthocyanidin 3-O-glucosyltransferase -> Chrysanthemin -> [1..9] 1) anthocyanin 3-O-glucoside-6’’-O- malonyltransferase -> Cyanidin 3-O-(6-O-malonyl-beta-D-glucoside) -> [1,2] 1) anthocyanidin 3-O-glucoside-3’’,6’’-O-dimalonyltransferase -> Cyanidin 3-O-3’’,6’’-O-dimalonylglucoside OR 2) cyanidin-3-O-glucoside 2’’-O- glucuronosyltransferase -> Cyanidin-3-O-(6’’-O-malonyl-2’’-O- glucuonyl)glucoside OR 2) cyanidin-3-O-glucoside 2’’-O- glucuronosyltransferase -> Cyanidin 3-O-(2-O-beta-D-glucuronosyl)-beta-D- glucoside OR 3) anthocyanidin 3-O-glucoside 2’’-O-glucosyltransferase -> Cyanidin 3-O-sophoroside OR 4)cyanidin 3-O-glucoside 7-O- glucosyltransferase (acyl-glucose) -> Cyanidin 3,7-di-O-beta-D-glucoside Hansford Boutchyard IV www.phytpharma.com 2/24/21 OR 5) Peonidin 3-glucoside OR 6) anthocyanidin 3-O-glucoside 2’’’-O- xylosyltransferase -> Cyanidin 3-O-beta-D-sambubioside -> anthocyanin 3-O- sambubioside 5-O-glucosyltransferase -> Cyanidin 5-O-beta-D-glucoside 3-O- beta-D-sambubioside OR 7) anthocyanidin-3-glucoside rhamnosyltransferase - > cyanidin 3-O-rutinoside -> [1,2] 1) cyanidin 3-O-rutinoside 5-O- glucosyltransferase -> Cyanidin 3-O-rutinoside 5-O-beta-D-glucoside OR 2) Cyanidin-3-(p-coumaroyl)-rutinoside-5-glucoside -> anthocyanin 3’- methyltransferase -> Peonidin-3-(p-coumaroyl)-rutinoside-5-glucoside OR 8) anthocyanidin 3-O-glucoside 6’’-O-acyltransferase -> Cyanidin 3-(6-p- caffeoyl)glucoside / Cyanidin 3-O-(6-O-p-coumaroyl)glucoside -> anthocyanidin 3-O-glucoside 5-O-glucosyltransferase -> Shisonin -> anthocyanin 5-O-glucoside-6’’’-O-malonyltransferase -> Malonylshisonin OR 9) anthocyanin 3-O-glucoside 5-O-glucosyltransferase & cyanidin 3-O- glucoside 5-O-glucosyltransferase (acyl-glucose) -> cyanin -> [1,2] 1) Shisonin -> anthocyanin 5-O-glucoside-6’’’-O-malonyltransferase -> Malonylshisonin OR 2) anthocyanin 5-aromatic acyltransferase -> [1,2] 1) Cyanidin 3-glucoside 5-coumarolyglucoside OR 2) Cyanidin 3-glucoside 5- caffeoylglucoside OR 2) anthocyanidin 5,3-O-glucosyltransferase -> cyanidin 5-O-glucoside -> anthocyanidin 5,3-O-glucosyltransferase -> cyanin -> [1,2] 1) Shisonin -> anthocyanin 5-O-glucoside-6’’’-O- malonyltransferase -> Malonylshisonin OR 2) anthocyanin 5-aromatic acyltransferase -> [1,2] 1) Cyanidin 3-glucoside 5-coumarolyglucoside 3) Delphinidin -> anthocyanidin 3-O-glucosyltransferase -> [1…9] 1) anthocyanidin 3-O-glucoside-6’’-O-malonyltransferase -> delphinidin 3-O- (6’’-O-malonyl)-beta-D-glucoside -> [1,2] 1) anthocyanidin 3-O-glucoside- 3’’,6’’-O-dimalonyltransferase -> Delphinidin 3-O-3’’,6’’-O- dimalonylglucoside OR 2) anthocyanidin 3’-O-beta-glucosyltransferase -> Delphinidin 3-O-(6’’-O-malonyl)-beta-D-glucoside-3’-O-beta-glucoside -> anthocyanidin 3’,5’-O-beta-glucosyltransferase -> Ternatin C5 -> Ternatin A1 OR 2) anthocyanidin 3-O-glucoside 2’’-O-glucosyltransferase -> Delphinidin 3-O-sophoroside OR 3) cyanidin 3-O-glucoside 7-O- glucosyltransferase (acyl-glucose) -> Delphinidin 3,7-di-O-beta-D- glucoside OR 4) Petunin 3-O-glucoside OR 5) Malvidin 3-O-glucoside OR 6) anthocyanidin 3-O-glucoside 2’’’-O-xylosyltransferase -> delphinidin 3-O- beta-D-sambubioside -> anthocyanin 3-O-sambubioside 5-O- glucosyltransferase -> Delphinidin 5-O-beta-D-glucoside 3-O-beta-D- sambubioside OR 7) delphinidin 3-O-glucoside + UDP-L-rhamnose Tulipanin +UDP -> Tulipanin -> Delphinidin-3-9p-courmaroyl)-rutinoside-5-glucoside -> Petunidin -3-(p-coumaroyl)-rutinoside-5-glucoside -> Malvidin-3-(p- coumaroyl)-rutinoside-5-glucoside OR 8) anthocyanidin 3-O-glucoside 6’’-O- acyltransferase -> [1,2] 1) Delphinidin 3-(6-p-coumaroyl)glucoside OR 2) Delphinidin 3-O-(6-p-caffeoyl)glucoside OR 9) anthocyanidin 3-O-glucoside 5-O-glucosyltransferase & cyanidin 3-O-glucoside 5-O-glucosyltransferase (acyl-glucose) -> Delphin -> [1,2] 1) anthocyanin 3’-O-beta- glucosyltransferase -> Delphinidin 3,5,3’-triglucoside -> Gentiodelphin OR 2) anthocyanin 5-aromatic acyltransferase -> Delphinidin 3-glucoside 5- coumaroylglucoside OR Delphinidin 3-glucose 5-caffoylglucoside -> Hansford Boutchyard IV www.phytpharma.com 2/24/21 anthocyanin 3’-O-beta-glucosyltransferase -> Albireodelphin -> Gentiodelphin Hansford Boutchyard IV www.phytpharma.com 2/24/21.