Anthocyanin Biosynthesis – https://www.kegg.jp/kegg-bin/highlight_pathway?scale=1.0&map=map00942&keyword=flavonoids

Anthocyanidins (aglycones) and (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, , , and , due to the different number of hydroxyl groups in the phenyl group. (Flavonoid Biosynthesis) -> [1,2,3]

1) Pelargonidin -> 3-O-glucosyltransferase -> Pelargonidin 3-O- glucoside -> [1,2,3,4,5,6,7] 1) 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) -> -> [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 -> -> [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) 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) 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  +UDP -> Tulipanin -> Delphinidin-3-9p-courmaroyl)-rutinoside-5-glucoside -> -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