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Page 1: Amino Acids - MIT OpenCourseWare€¦ · Amino acids and nucleic acids NMe HN O OH H H N N N N O O CH3 CH3 H3C N Me O CO2Me O pseudopelletierine nicotine N N H Me caffeine ergot O
Page 2: Amino Acids - MIT OpenCourseWare€¦ · Amino acids and nucleic acids NMe HN O OH H H N N N N O O CH3 CH3 H3C N Me O CO2Me O pseudopelletierine nicotine N N H Me caffeine ergot O

Amino Acids:OrnithineLysineTyrosineTryptophan

Purine

Starting materials:Amino acids and nucleic acids

NMe

HN

OHO

H

H

N

N N

N

O

O

CH3

CH3

H3C

NMe O

CO2Me

O

pseudopelletierine

nicotineN

NMeH

caffeine

ergot

O

NCH3

HO

HO

HH

morphine

CO2

NH3

OH

NH

NH3

CO2

N

NN

N

NH2

O

OHOH

OP-O

O-

O

NH3

CO2

H3N

CO2

H3N

NH3

NMe

O

cocaine

ornithine

purine

tyrosine

lysine

tryptophan

5.451 F2005Alkaloid Biosynthesis:Nitrogen containing compounds

(fungus)

rebeccamycinstaurosporine

Page 3: Amino Acids - MIT OpenCourseWare€¦ · Amino acids and nucleic acids NMe HN O OH H H N N N N O O CH3 CH3 H3C N Me O CO2Me O pseudopelletierine nicotine N N H Me caffeine ergot O
Page 4: Amino Acids - MIT OpenCourseWare€¦ · Amino acids and nucleic acids NMe HN O OH H H N N N N O O CH3 CH3 H3C N Me O CO2Me O pseudopelletierine nicotine N N H Me caffeine ergot O

5.451 F2005Alkaloid Biosynthesis:Purine Derived Products: Caffeine

T

Figure removed due to copyright reasons. Please see Figure 4 in Trends Plant Sci 6 (2001): 407.

Page 5: Amino Acids - MIT OpenCourseWare€¦ · Amino acids and nucleic acids NMe HN O OH H H N N N N O O CH3 CH3 H3C N Me O CO2Me O pseudopelletierine nicotine N N H Me caffeine ergot O

5.451 F2005Alkaloid Biosynthesis:Purine Derived Products: Caffeine

Genetically engineered decaf coffee

70% reduction in caffeine content by using RNAi of theobromine synthase

otherwise normal phenotype

Nature (2003) 423, 823

Recently discovered natural variant deficient in caffeine synthase

Nature (2004) 429, 826.

Promoter of the 3 methyl transferases recently discovered

J. Biotech. (2005) 119, 20-25.

Page 6: Amino Acids - MIT OpenCourseWare€¦ · Amino acids and nucleic acids NMe HN O OH H H N N N N O O CH3 CH3 H3C N Me O CO2Me O pseudopelletierine nicotine N N H Me caffeine ergot O

pyrrolizidine

5.451 F2005Alkaloid Biosynthesis:Ornithine and Lysine Derived Products

N

H

homospermidine(via 2 putrescines)

tropanes

NMe

nicotineN

NMeH

quinolizidines

N

indolizidines

N

NH2H2N

putrescine (via ornithine)2 acetates

NH2H2N

putrescine (via ornithine)nicotinic acid

NMe

pseudopelletierine

cadaverine (via lysine)2 acetates

2 cadaverines pipecolic acid (via lysine)1 acetate

Page 7: Amino Acids - MIT OpenCourseWare€¦ · Amino acids and nucleic acids NMe HN O OH H H N N N N O O CH3 CH3 H3C N Me O CO2Me O pseudopelletierine nicotine N N H Me caffeine ergot O
Page 8: Amino Acids - MIT OpenCourseWare€¦ · Amino acids and nucleic acids NMe HN O OH H H N N N N O O CH3 CH3 H3C N Me O CO2Me O pseudopelletierine nicotine N N H Me caffeine ergot O
Page 9: Amino Acids - MIT OpenCourseWare€¦ · Amino acids and nucleic acids NMe HN O OH H H N N N N O O CH3 CH3 H3C N Me O CO2Me O pseudopelletierine nicotine N N H Me caffeine ergot O

pyrrolidines nicotine

N

NMeHN

H

5.451 F2005 Alkaloid Biosynthesis:Ornithine Derived Products

N

CO2H

N

OH

O

NH N

H

H

NMeH

NMeH

NMe

H-

H+

H+

NADP+

CO2

nicotinic acid

B3 (niacin)

Page 10: Amino Acids - MIT OpenCourseWare€¦ · Amino acids and nucleic acids NMe HN O OH H H N N N N O O CH3 CH3 H3C N Me O CO2Me O pseudopelletierine nicotine N N H Me caffeine ergot O

pyrrolizidine

5.451 F2005 Alkaloid Biosynthesis:Ornithine Derived Products

N

H

Page 11: Amino Acids - MIT OpenCourseWare€¦ · Amino acids and nucleic acids NMe HN O OH H H N N N N O O CH3 CH3 H3C N Me O CO2Me O pseudopelletierine nicotine N N H Me caffeine ergot O

pyrrolizidine

5.451 F2005 Alkaloid Biosynthesis:Ornithine Derived Products

N

H

PNAS (1999) 96, p. 14779

Origin of a secondary metabolic pathway?Found only in angiosperms

NH

H2NNH2

H2N NH2NH

H2NNH2+

NH2E

NH

H2NNH2+

HN

E NH2

E = elF5A

HN

E NH2

OH

hypusine

deoxyhypusine

spermidine

lysine of transcription factor

putrescine homosperrmidine

HS synthase

DH synthase

deoxyhypusinesynthase

Page 12: Amino Acids - MIT OpenCourseWare€¦ · Amino acids and nucleic acids NMe HN O OH H H N N N N O O CH3 CH3 H3C N Me O CO2Me O pseudopelletierine nicotine N N H Me caffeine ergot O

piperidines ornithine

5.451 F2005 Alkaloid Biosynthesis:Lysine Derived Products

NH

H3N CO2

NH2

H3N CO2

NH2

lysine

Page 13: Amino Acids - MIT OpenCourseWare€¦ · Amino acids and nucleic acids NMe HN O OH H H N N N N O O CH3 CH3 H3C N Me O CO2Me O pseudopelletierine nicotine N N H Me caffeine ergot O

quinolizidines

5.451 F2005 Alkaloid Biosynthesis:Lysine Derived Products

N

N

H2N NH2 H2N CHONH NH

NH

NH

HNH

CHOH

NH2

NH

CHOH

CHO

CHOH

NH2H2N

NH

H2N

N

NH2H2N NH2

NH

OHC NH2OHC

N

HCHO

N

H2N

Page 14: Amino Acids - MIT OpenCourseWare€¦ · Amino acids and nucleic acids NMe HN O OH H H N N N N O O CH3 CH3 H3C N Me O CO2Me O pseudopelletierine nicotine N N H Me caffeine ergot O

indolizidines

5.451 F2005 Alkaloid Biosynthesis:Lysine Derived Products

N

H3N NH2NH N

CO2

H2N H

CO2 O

CO2H

NH

O O

SCoAH H O

O

O

OH O

MeOO

O

N

HO

MeO

OO

OH H

OMe

pipecolic acid acetate

polyketide/peptiderapamycin

cyclohexylCoA

shikimicacid

Page 15: Amino Acids - MIT OpenCourseWare€¦ · Amino acids and nucleic acids NMe HN O OH H H N N N N O O CH3 CH3 H3C N Me O CO2Me O pseudopelletierine nicotine N N H Me caffeine ergot O

5.451 F2005 Alkaloid Biosynthesis:Ornithine Derived Products

Source of alkaloidsarthropod eats plant;or ant or symbiontof ant makes alkaloidvertebrate (frog) eats ant

after injestion, can be derivatized by frog to make more poisonousSee Figure 1 in PNAS 100 (2003): 11092.

alkaloids found in ants and frogsSee Figure 1 in PNAS 101 (2004): 8045.

Figure removed due to copyright reasons.

Figure removed due to copyright reasons.

Page 16: Amino Acids - MIT OpenCourseWare€¦ · Amino acids and nucleic acids NMe HN O OH H H N N N N O O CH3 CH3 H3C N Me O CO2Me O pseudopelletierine nicotine N N H Me caffeine ergot O

5.451 F2005 Alkaloid Biosynthesis:Ornithine Derived ProductsChemical Defense

Figures removed due to copyright reasons.

Page 17: Amino Acids - MIT OpenCourseWare€¦ · Amino acids and nucleic acids NMe HN O OH H H N N N N O O CH3 CH3 H3C N Me O CO2Me O pseudopelletierine nicotine N N H Me caffeine ergot O

5.451 F2005 Alkaloid Biosynthesis:Ornithine Derived Products

Removed due to copyright reasons.

Page 18: Amino Acids - MIT OpenCourseWare€¦ · Amino acids and nucleic acids NMe HN O OH H H N N N N O O CH3 CH3 H3C N Me O CO2Me O pseudopelletierine nicotine N N H Me caffeine ergot O

pyrrolizidine

5.451 F2005 Alkaloid Biosynthesis:Ornithine Derived ProductsOutwitting the Chemical Defense- Detoxification by oxidation

N

H

N

HCHO

O

detoxification

Figure removed due to copyright reasons. Please see Figure 1 in PNAS 99 (2002): 6085.


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