Biological reaction Biomass Polysaccharides Multiple biological reactions Potential beachhead molecule

HO OH This map represents a compilation of metabolic pathways that have been described Glycolic acid HO HO 1 HO HO for conversion of biomass-derived polysaccharides to industrial chemicals. HO OH O O OH OOH O O O OH O HO OH OH OH OH HO Adapted by permission from Springer Nature Customer Service Centre GmbH: OH OH OH OH OH OH HO OH OH Ethylene glycol Nature, Nature Calalysis, A comprehensive metabolic map for production of bio- OH OH OH OH L-Arabinose Galactose Glucose D-Xylose D-xylono-1,4-lactone Xylonic acid OH OH OH based chemicals, Lee, S.Y., et al., 2019 HO HO 1,2,4-Butanetriol 1,4-Butanediol

O OH OH HO OH HO OH O O HO OH HO O OH CoA S OH OH Xylitol HO NH2 HO Propanol Resveratrol Lactaldehyde Malonyl-CoA 4-Hydroxyhexan-3-one HO OH Benzyl alcohol

-O Hydroxytyrosol HO O O O CoA S O OH O -O O N HO OH OH O O OH H O 4-phenylbutyrate O OH HO Benzene O O Hippurate Acetol Methylglyoxal Ferulic acid p-Coumaroyl-CoA OH O Propanal 1,2-Propanediol HO 4-Hydroxy-2-oxohexanoic acid p-Hydroxystyrene HO NH2 Benzaldehyde HO OH OH OH Dopamine O OH 1,3-Propanediol O O O O O P - OH O HO O O 2 HO HO HO Glycerone HO OH OH O HO HO 6-phenylhexanoate OH cis, cis-Muconic acid HO O OH O Glyceraldehyde OH HO OH OH HO O O O P - Benzoic acid 3-Phosphate Dihydrobenzenediol Caffeic acid p-Coumaric acid O OH HO 1,3-propanediol 3-Hydroxypropanal HO O HO OH HO NH Glycerol O 2 OH O HO NH2 O HO O P OH Dihydroxyacetone phosphate O OH (R)-Mandelate Pentose L-DOPA phosphate 4 HO HO OH OH Tyramine Phenylacetic acid pathway 3-Hydroxypropionic acid Glycerol-3-phosphate HO NH2 HO O OH HO O O OH O O HO HO OH HO HO OH HO L-Tyrosine O HO O O OH OH Catechol O Phenol OH Phenylglyoxylate Acrylic acid 3-Hydroxypropionic acid D-Glyceraldehyde D-Glycerate O HO O Phenyl acetaldehyde Phenylethanol O O O HO HO NH2 OH HO O OH O O O HO OH O- OH O O O H2N 2-Pyrone- 4-Hydroxyphenyllactic Toluene O O β-ketoadipic acid OH O O O HO OH OH O O 4,6-dicarboxylic acid acid Tyrosol OH OH O O P OH P (S)-Mandelate OH H2N H N HO O P OH NH2 OH 2 O OH NH2 OH O OH OH OH OH D-Phenylglycine O O L-Phenylglycine NH2 O Glycine 3-Phospho- 5 4,5-Dioxopentanoate 5-Aminolevulinate L-Serine O-Phospho-L-serine O 3-Phosphooxypyruvate 3 OH HO D-glycerate OH HO HO O O OH H2N OH O O O O O O O OH H2N OH HO HO OH HO 2-Butanol NH2 OH Protocatechuic acid Vanillin 4-Hydroxyphenylacetic acid Prephenic acid Phenylpyruvate L-Phenylalanine Phenethylamine Ethanolamine HO O HO HO P O O O OH HO O O OH O OH O O O O OH 4-methyl-1-pentanol OH * * HO D-Erythrose 4-phosphate HO OH OH O O S CoA HO OH trans-Cinnamic acid HO O O 4-Hydroxymandelic acid Phenyllactic acid Poly(3HB-co-PhLA) Propanol Propionyl-CoA Butanone Meso-2,3-Butanediol 3-Methyl-1-butanol 2-Ketoisoheptanoate Isocaproate HO OH 6 HO CoA HO HO O O S O OH OH O O OH HO O P HO HO HO OH O O HO O OH HO O O O OH OH O O HO HO HO HO 3-Deoxy-D-arabino- O HO 4-Hydroxybenzoic acid 4-Hydroxybenzoate-CoA Styrene HO O OH Shikimic acid Chorismate O heptulosonate-7-phosphate 3-Dehydroshikimate O HO O O OH OH O P OH (S,S)-2,3-Butanediol (R,R)-2,3-Butanediol 2-Ketoisocaproate Isovalerate 3-Hydroxyisovalerate HO NH2 HO S CoA OH O HO HO O O O 4-Aminobenzoic acid NH2 Acrylyl-CoA Propionic acid O O Phosphoenolpyruvate HO OH OH O HO NH2 HO HO Danshensu O * Isobutanol 4-aminophenylacetic acid OH * 4-aminophenylpyruvate H2N O - n 8 O O O O H 7 Isochorismate Poly(4-hydroxybenzoate) NH HO O 2 O OH OH O O Anthranilate O NH 2 O HO - NH2 HO O NH HO 4-aminophenylacetaldehyde O NH2 OH 2 O O O O O O (S)-Acetoin Acetolactate 2-Ketoisovalerate HO NH NH2 (R)-acetoin L-Valine HO 2 N S CoA OH N N H NH H 2 4-aminophenylalanine OH OH O L-Tryptophan Serotonin 5-methoxytryptamine H2N OH O Acrylic acid HO 4-aminophenylethanol Lactyl-CoA NH Lactic acid O Aniline L-Leuc2ine HO OH H H2N N O NH2 NH2 9 H O O Isopentane Isobutyrate N 4-aminocinnamic acid 4-aminophenylethylamine O O O O OH CO2 + H2 S CoA HO O Melatonin HO OH Formic acid O O O O O n 4-Methylpentanoic acid Isobutyryl-CoA O 4-methyl-1-pentanol Pyruvate Polylactic acid HO S CoA S CoA HO O HO S CoA Ethanol )-3-Hydroxybutyryl-CoA Crotonoyl-CoA Butyryl-CoA 1-Butanol O (S HO O O O Isobutyl acetate HO HO O OH 10 HO Isobutanol O OH O O R S ACP O Acetaldehyde O Adipic acid R S ACP Isoamyl acetate HO 2-Hydroxyisobutyrate Acyl-ACP OH O O OH O O OH O Enoyl-ACP R OH O O Citramalate Hexanoic acid Pentane S ACP S CoA OH Fatty alcohol HO HO S CoA (C5 or longer) Acetoacetyl-CoA O HO O (R)-3-Hydroxybutyryl-CoA (R)-3-Hydroxybutyrate R OEt Acetyl-ACP 3-Methyl-1-butanol Acetate O OH OH FAEE Butyrate HO OH O O HO Octanoic acid O O 1,3-Butanediol R O O O OH O acetone Isopropanol R OMe HO S ACP11 Fatty acids HO S CoA FAME 12 OH Malonyl-CoA Malonyl-ACP S CoA HO Propane O HO R O O HO Prenol Myrcene Farnesene Acetyl-CoA Geranylgeraniol Alkene OH OH O OH R S ACP OH R Mevalonic acid Geraniol Limonene Farnesol R S ACP Alkane β-Keto acyl-ACP O O Santalene β-Hydroxy acyl-ACP (C7 or longer) O H HO OH HO O HO O OHO O O O P P P 3-Hydroxypropionic acid 3-Pentanone 2-Butanone Pentadecaheptaene O O OH O O O O P O O O P OH O P H H P P HO O O O Isoprene O OHO H OH HO Isopentenenyl Geranyl Farnesyl Geranylgeranyl O O O diphosphate diphosphate diphosphate NH diphosphate 2 S Kaurene HO O HO NH2 O O OH NH2 O O OH NH 13 Ethylene 1-Aminocyclopropane-1- 2 OH O O O 15 carboxylic acid HO OH HO 16 O L-Methionine O Malonic acid OH Oxaloacetate HO OH H H OH 17 O β-Alanine OH OH NH2 O HO HO H2N Citrate OH H2N NH2 L-Aspartate Isoprenol Pinene Sabinene Artemisinic acid β-Carotene Propanol Propionic acid L-Homoalanine OH 1,3-Diaminopropane 14 O OH O OH O Cineole Bisabolene HO O NH2 NH2 OH OH OH OH O HO HO HO NH2 1,2,4-Butanetriol HO O 18O HO O H OH O OH O O HO HO H2N N O NH2 HO O HO - O O O OH NH NH O O Itaconic acid cis-Aconitate O NH OH O O H N N Astaxanthin L-Isoleucine 2-Ketobutyric acid L-Threonine Homoserine OH 2 L-Homocarnosine 4-Guanidinobutanoate Aspartate OH HO semialdehyde HO Malate 1-Butanol O O O OH OH HO HO O OH 2,4-Dihydroxybutyrate O 2-Methyl-1-butanol OH NH2 O H2N NH2 OH O HO O O O 3-Methyl-1-pentanol L-2-Aminoadipate O O OH O O HO H2N OH OH N γ-Aminobutyric acid 4-Aminobutyraldehyde OH Glyoxylate HO Isocitrate H O OH O H2N γ-Aminobutyric acid Butyrolactam H2N H2N O20 HO (E)-2-Methyl-2-pen19tenoic acid NH2 O HO OH O OH O 4-Hydroxyvaleric acid NH H2N O 2 Tiglic acid OH Oxalic acid Ethylene O H2N OH HO OH HN P HO NH2 L-β-Lysine O O OH O HO O O HO L-Lysine L-ɑ-Aminocaprolactam HO O O O O 22 D-Glucosamine 6- OH L-Glutamine O S CoA phosphate Propionyl-CoA O OH HO OH 2-Methylpentanoic acid HO HO O HO NH2 O O O 2-Methylbutyric acid OH Fumarate O HO O- O OH NH2 Levulinic acid H2N O HO N HO NH H2N HO 6-Hydroxyhexanoic acid ɑ-Ketoglutarate 2 O O O H H2N NH2 NH2 Putrescine HO O O 2,3-Dihydroxybutyrate L-Glutamate N-Acetyl-L-ornithine Cadaverine L-Ornithine O β-Hydroxy-ɣ- OH H2N O O Heptanoic acid butyrolactone O O Pentanoic acid NH2 OH O O HN HO S CoA Propionic acid HO O NH2

5-Aminopentanamide S CoA H O O HO O HO H N N OH

O OH H 2

Methylmalonyl-CoA OH O NH2 NH2 O O HO O NH2 N OH OH O Succinyl-CoA O O N-Carbamoyl putrescine ɑ-Ketoglutarate semialdehyde 6-Aminocaproic acid Citrulline Butane Glycolic acid OH Succinic acid O O OH L-Proline Lactic acid O N O - O H2N O 23 L-1-Pyrroline- H21O O OH O

O OH OH O 5-carboxylate NH2 HN

3-Pentanone 5-Methyl-3-hexanone O HO HO HO H2N HN O O O N N

HN Adipic acid OH OH H H

O O HO OH O N O NH NH OH HN 2 2 Valerolactam 5-Aminovaleric acid OH OH O OH HO O Glycolaldehyde Arginosuccinate Agmatine 2-Dehydro-3-deoxy- 2-Dehydro-3-deoxy- Caprolactam O N Succinate semialdehyde OH O L-arabinonate D-arabinonate H O D-Proline L-Hydroxyproline O n m NH2 25 O O O OH O O Poly(lactic-co-glycolic acid) HO OH O OH O

O O O N O N

H2N O NH2 O OH HO OH OH HO O

O OH H

O OH OH OH H2N N OH 24H2N HN - OH HO OH HO OH Ethylene glycol O HO HO HO OH OH O NH Glutarate semialdehyde O S CoA OH NH O Suberic acid Glutaric acid D-Xylonate L-Arabinoate 1-Pyrroline- NH O 4-Hydroxybutyryl-CoA 4-Hydroxybutyric acid 2-carboxylate 5-Aminovaleric acid Proclavaminate L-Arginine Gamma-butyrolactone Feruloylagmatine

HO HO O O OH HO O OH O OH O O O O OH OH NH2 HO OH O HN HO O OH NH H OH H2N N H2N N OH O HO OH H2N N OH OH OH HO O Sebacic acid 7-Hydroxyheptanoic acid Pimelic acid OH OH NH2 O HO O NH O D-Xylose L-Arabinose Octopine 2-Oxoarginine Nopaline 1,4-Butanediol 4-Hydroxybutyraldehyde