Classification

Bufotenin, a poison from some toads, contains an indole core and is produced in living
organisms from the amino acid tryptophan.

The nicotine molecule contains both pyridine (left) and pyrrolidine rings (right).

Compared with most other classes of natural compounds, alkaloids are characterized by a
great structural diversity and there is no uniform classification of alkaloids.[24]
Historically, first classification methods combined alkaloids by the common natural
source, e.g., a certain type of plants. This classification was justified by the lack of
knowledge about the chemical structure of alkaloids and is now considered obsolete.[5][25]

More recent classifications are based on similarity of the carbon skeleton (e.g., indole,
isoquinoline and pyridine-like) or biogenetic precursor (ornithine, lysine, tyrosine,
tryptophan, etc.).[5] However, they require compromises in borderline cases;[24] for
example, nicotine contains a pyridine fragment from nicotinamide and pyrrolidine part
from ornithine[26] and therefore can be assigned to both classes.[27]

Alkaloids are often divided into the following major groups:[28]

1. "True alkaloids", which contain nitrogen in the heterocycle and originate from
amino acids.[29] Their characteristic examples are atropine, nicotine and morphine.
This group also includes some alkaloids which beside nitrogen heterocycle
contain terpene (e.g. evonine[30]) or peptide fragments (e.g. ergotamine[31]). This
group also includes piperidine alkaloids coniine and coniceine[32] although they do
not originate from amino acids.[33]
2. "Protoalkaloids", which contain nitrogen and also originate from amino acids.[29]
Examples include mescaline, adrenaline and ephedrine.
3. Polyamine alkaloids – derivatives of putrescine, spermidine and spermine.
4. Peptide and cyclopeptide alkaloids.[34]
 5. Pseudalkaloids – alkaloid-like compounds which do not originate from amino
acids.[35] This group includes, terpene-like and steroid-like alkaloids,[36] as well as
purine-like alkaloids such as caffeine, theobromine and theophylline.[37] Some
authors classify as pseudoalkaloids such compounds such as ephedrine and
cathinone. Those originate from the amino acid phenylalanine, but acquire their
nitrogen atom not from the amino acid but through transamination.[37][38]

Some alkaloids do not have the carbon skeleton characteristic of their group. So,
galantamine and homoaporphines do not contain isoquinoline fragment, but are generally
attributed to isoquinoline alkaloids.[39]

Main classes of monomeric alkaloids are listed in the table below:

Class Major groups Main synthesis steps Examples

Alkaloids with nitrogen heterocycles (true alkaloids)
Pyrrolidine Ornithine or arginine
derivatives[40] → putrescine → N-
Hygrine, hygroline,
methylputrescine →
stachydrine[40][42]
N-methyl-Δ1-
pyrroline [41]
Tropane Atropine group Atropine,
derivatives[43] Substitution in positions 3, 6 or Ornithine or arginine scopolamine,
7 → putrescine → N- hyoscyamine[40][43][44]
methylputrescine →
Cocaine group N-methyl-Δ1- Cocaine, ecgonine [43]
[41]
Substitution in positions 2 and 3 pyrroline [45]

Retronecine,
Non-esters In plants: ornithine or heliotridine,
arginine → laburnine [46][47]
Complex esters of putrescine → Indicine, lindelophin,
Pyrrolizidine monocarboxylic acids homospermidine → sarracine [46]
derivatives[46] retronecine [41] Platyphylline,
Macrocyclic diesters
trichodesmine[46]
In fungi: L-proline +
L-homoserine → N- Loline, N-
1-aminopyrrolizidines
(3-amino-3- formylloline, N-
(lolines)
carboxypropyl)prolin acetylloline[50]
e → norloline[48][49]
Piperidine Sedamine, lobeline,
Lysine → cadaverine
derivatives[51] anaferine, piperine
→ Δ1-piperideine [52] [32][53]
Octanoic acid →
Coniine, coniceine
coniceine → coniine [33]
[33]
 Lupinine, nupharidin
Lupinine group [54]

Quinolizidine Cytisine group Cytisine [54]

derivatives[54][55]
Sparteine group
Matrine group
Ormosanine group
Indolizidine
derivatives[60]
Simple derivatives of
pyridine
Sparteine, lupanine,
Lysine → cadaverine
anahygrine[54]
→ Δ1-piperideine [56]
Matrine, oxymatrine,
allomatridine[54][57][58]
Ormosanine,
piptantine[54][59]
Lysine → δ-
semialdehyde of α-
Swainsonine,
aminoadipic acid →
castanospermine [62]
pipecolic acid → 1
indolizidinone [61]
Trigonelline,
ricinine, arecoline [63]
[66]

Nicotinic acid → Nicotine,

Pyridine Polycyclic noncondensing digidronikotinovaya nornicotine,
derivatives[63][64]
pyridine derivatives acid → 1,2- anabasine, anatabine
dihydropyridine [65] [63][66]
Actinidine,
Polycyclic condensed
gentianine,
pyridine derivatives
pediculinine [67]
Evonine,
Sesquiterpene pyridine Nicotinic acid,
hippocrateine,
derivatives isoleucine [11]
triptonine [64][65]
Isoquinoline Simple derivatives of Tyrosine or Salsoline,
[69]
derivatives and isoquinoline phenylalanine → lophocerine [68][69]
related alkaloids dopamine or N-methylcoridaldine,
[68] Derivatives of 1- and 3- tyramine (for noroxyhydrastinine
isoquinolines [72] alkaloids Amarillis) [72]
[70][71]
Derivatives of 1- and 4-
phenyltetrahydroisoquinoli Cryptostilin [69][73]
[69]
nes
Derivatives of 5-naftil-
Ancistrocladine [74]
isoquinoline [74]
Papaverine,
Derivatives of 1- and 2-
laudanosine,
benzyl-izoquinolines [75]
sendaverine
Cularine, yagonine
Cularine group[76] [76]

Argemonine,
Pavines and isopavines [77]
amurensin [77]
Benzopyrrocolines [78] Cryptaustoline [69]
 Berberine, canadine,
ophiocarpine,
Protoberberines [69]
mecambridine,
corydaline [79]
Hydrastine, narcotine
Phtalidisoquinolines [69]
(Noscapine) [80]
Spirobenzylisoquinolines
[69] Fumaricine [77]
Emetine,
[81]
Ipecacuanha alkaloids protoemetine,
ipecoside [81]
Sanguinarine,
Benzophenanthridines [69] oxynitidine,
corynoloxine [82]
Glaucine, coridine,
Aporphines [69]
liriodenine [83]
Pronuciferine,
Proaporphines [69]
glaziovine [69][78]
Kreysiginine,
Homoaporphines [84]
multifloramine [84]
Homoproaporphines [84] Bulbocodine [76]
Morphine, codeine,
Morphines[85] thebaine, sinomenine
[86]

Kreysiginine,
Homomorphines [87]
androcymbine [85]
Tropoloisoquinolines [69] Imerubrine [69]
Rufescine,
Azofluoranthenes [69]
imeluteine [88]
Lycorine, ambelline,
tazettine,
Amaryllis alkaloids[89]
galantamine,
montanine [90]
Erysodine,
Erythrite alkaloids[73]
erythroidine [73]
Phenanthrene derivatives Atherosperminine [69]
[69] [79]

Protopine,
[69]
Protopins oxomuramine,
corycavidine [82]
Aristolactam [69] Doriflavin [69]
Oxazole Tyrosine → tyramine Annuloline,
derivatives[91] [92]
halfordinol, texaline,
texamine[93]
Thiazole
derivatives[94] 1-Deoxy-D-xylulose
5-phosphate Nostocyclamide,
(DOXP), tyrosine, thiostreptone [94][96]
cysteine [95]

Quinazoline 3,4-Dihydro-4-quinazolone
Febrifugine[99]
derivatives[97] derivatives
Anthranilic acid or
1,4-Dihydro-4-quinazolone Glycorine, arborine,
phenylalanine or
derivatives glycosminine[99]
ornithine [98]
Pyrrolidine and piperidine Vazicine (peganine)
[91]
quinazoline derivatives
Acridine
derivatives[91] Rutacridone,
Anthranilic acid [100]
acronicine[101][102]

Simple derivatives of
Cusparine,
quinoline derivatives of 2 -
echinopsine,
quinolones and 4-
evocarpine[104][106][107]
quinolone Anthranilic acid →
Tricyclic terpenoids 3-carboxyquinoline Flindersine[104][108]
Quinoline [105]
Dictamnine,
derivatives[103][104] Furanoquinoline fagarine,
derivatives skimmianine[104][109]
[110]

Tryptophan →
tryptamine →
Quinine quinidine
strictosidine (with
Quinines cinchonine,
secologanin) →
cinhonidine [108]
korinanteal →
cinhoninon [71][105]
Indole Non-isoprene indole alkaloids
derivatives[86] Tryptophan → Serotonin,
tryptamine or 5- psilocybin,
Simple indole derivatives [112]
[111] hydroxitriptofan dimethyltryptamine
(DMT), bufotenin
[113][114]

See also: indole Simple derivatives of β- Harman, harmine,

carboline [115] harmaline, eleagnine
 [111]

Physostigmine
(eserine),
Pyrroloindole alkaloids [116] etheramine,
physovenine,
eptastigmine[116]
Semiterpenoid indole alkaloids
Tryptophan →
chanoclavine →
Ergotamine,
agroclavine →
Ergot alkaloids[86] ergobasine,
elimoclavine →
ergosine[117]
paspalic acid →
lysergic acid [116]
Monoterpenoid indole alkaloids
alkaloids Ajmalicine,
sarpagine, vobasine,
ajmaline, yohimbine,
reserpine,
Corynanthe type
mitragynine [118][119],
alkaloids[112]
group strychnine and
Tryptophan → (Strychnine brucine,
tryptamine → aquamicine,
strictosidine (with vomicine [120])
secologanin) [112]
Ibogamine, ibogaine,
Iboga-type alkaloids[112]
voacangine[112]
Vincamine,
Aspidosperma-type vincotine,
alkaloids[112] aspidospermine[121]
[122]

Imidazole
derivatives[91] Histamine,
Directly from
pilocarpine, pilosine,
histidine[123]
stevensine[91][123]

Purine Xantosine (formed in

derivatives[124] purine biosynthesis) Caffeine
→ 7 methylxantosine theobromine
→ 7-methyl xanthine theophylline
→ theobromine → saxitoxin [125][126]
caffeine [71]
Alkaloids with nitrogen in the side chain (protoalkaloids)
β- Tyrosine or Tyramine, ephedrine,
Phenylethylamine phenylalanine → pseudoephedrine,
[78]
derivatives dioxyphenilalanine mescaline, cathinone,
→ dopamine → catecholamines
 adrenaline and
mescaline tyrosine →
tyramine
phenylalanine → 1- (adrenaline,
phenylpropane-1,2- noradrenaline,
dione → cathinone dopamine)[11][128]
→ ephedrine and
pseudoephedrine [11]
[38][127]

Colchicine
alkaloids [129] Tyrosine or
phenylalanine →
Colchicine,
dopamine →
colchamine[129]
autumnaline →
colchicine [130]

Muscarine [131]
Glutamic acid → 3- Muscarine,
ketoglutamic acid → allomuscarine,
muscarine (with epimuscarine,
pyruvic acid)[132] epiallomuscarine[131]

Benzylamine[133] Capsaicin,
Phenylalanine with
dihydrocapsaicin,
valine, leucine or
nordihydrocapsaicin
isoleucine[134] [133][135]

Polyamines alkaloids
Putrescine
derivatives[136] Paucine [136]

Spermidine ornithine →
derivatives[136] putrescine → Lunarine,
spermidine → codonocarpine[136]
spermine[137]
Spermine
derivatives[136] Verbascenine,
aphelandrine [136]

Peptide (cyclopeptide) alkaloids

Peptide alkaloids From different amino Numularine C,
Numularine C type
with a 13- acids [34] numularine S [34]
membered cycle Ziziphin A,
[34][138] Ziziphin type
sativanine H [34]
Peptide alkaloids Frangulanine,
Frangulanine type
with a 14- scutianine J [138]
membered cycle Scutianine A type Scutianine A [34]
[34][138]
Integerrine type Integerrine, discarine
 D [138]
Amphibine F,
Amphibine F type
spinanine A [34]
Amphibine B,
Amfibine B type
lotusine C [34]
Peptide alkaloids
with a 15-
Mucronine A type Mucronine A [31][138]
membered cycle
[138]

Pseudoalkaloids (terpenes and steroids)

[31]
Diterpenes Mevalonic acid →
izopentenilpyrophosf Aconitine, delphinine
Licoctonine type [31][141]
ate → geranyl
[139][140]
pyrophosphate
Steroids[142]
Solasodine,
Cholesterol,
solanidine,
arginine[143]
veralkamine[144]