the maillard reaction literature meeting lucie zimmer january the 30 th 2007
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The Maillard Reaction
Literature Meeting
Lucie Zimmer
January the 30th 2007
Caramel (sugars)
Cream(amino compounds)
Browning
• Brown or black pigments
• Characteristic odour and taste
• Alteration of Nutritive properties
• Browning of banana / reding of pasta
Maillard Reaction
• From the name of the french chemist, Louis-Camille Maillard
• Main steps published in 1912 but still studied.
• Lead to the formation of many organoleptic compounds
• Antioxydative and carcinogenic properties of Maillard products
Very versatile reaction (schizophrenic?)
HN
N
N
N
O
N
N O
N
N
O
2-ethyl-3-methoxypyrazinePotatoes
2-ethyl-2,3-dimethyl-1,2-dihydropyrazineRoasted Almond
N
N
2-ethyl-3,6-dimethyl-pyrazineHazelnut
formylpyrazineToasted smell
2-ethoxy-3-methylpyrazineRoasted Walnut
Maillard Reaction : main steps
Bristow, M.; Isaacs, N. S. J. Chem. Soc., Perkin Trans. 2, 1999, 2213-2218
Maillard Reaction : main steps
• Three main steps
– Maillard condensation and Amadori rearrangement
– Formation of caracteristic compounds
– Melanoidin formation
Machiels, D.; Istasse, L. Ann. Med. Chem. 2002, 146, 347-352.
Aldose, cetose… Every reductive
sugars
Amino acids, peptides, proteines
N-substitued glycosylamines
Stable if from proteines or peptides
If from aminoacids : Amadori
rearrangement
I. Condensation de Maillard
Reaction easier with small sugar and amine function far from carboxylic acid moeity.
(special case of lysine: rate 5-15 times higher)
CHO
OHH
HHO
OHH
OHH
CH2OH
+ COOHH2N
R
OHH
HHO
OHH
OHH
CH2OH
N
R'
O
H
HO
H
HO
H
NHOHH H
OH
R'
- H2Ocondensation
I. Amadori and Heyns rearrangements
Amadori rearrangement :
Application: transformation of aldose in ketose and ketose in aldose
Heyns rearrangement : (A bit slower)
HO
OH
HO OH
NOH
HOOCR
HO
OH
HO OH
HNOH
HOOCR
O
OH
HO OH
HNOH
HOOCR
Imine / enamine enol / aldehyde
Fructose(open form) 2-amino-2-desoxyaldose
from ketoses
O
H
HO
H
HO
H
NHOHH H
OH
R'
OH
H
HO
H
HO
H
NHOHH H
OH
R'
Lewis or protic acidOH
H
HO
H
HO
NHOHH H
OH
R'
OH
H
HO
H
HO
NHOH H
OH
R'
- H+
from aldoses
II. CHARACTERISTIC COMPOUND
FORMATION
II. Characteristic compounds: formation
1. Scission:
Formation of small molecules : retroaldol cleavage.
Those molecule can react by aldolic condensation to give polymeres.
Ledl, F.; Scleicher, E. Angew. Chem. Int. Ed. 1990, 29, 565-705.
H H
O
OHH
O
H
O
H
O
O
OH
H
O
O
OH
O
HO HO
O
H
O O
O
OH
O
O
HO
OH
OH
O
H
O
OH
NH2
O
NH2
OH
OH
H
HO
H
HO
NHOH
H
OH
R'
1. Scission:
recombination of the small molecules
Ledl, F.; Scleicher, E. Angew. Chem. Int. Ed. 1990, 29, 565-705.
O
N
O
OH HO
HO
H
O
H
O
NO N
HO H
O
N
N
O
O
N
OH
O
O
O NH
O
II. Characteristic compounds: formation
2. 1,2 or 2,3 enolisation followed by dehydratation:
2.1 Low or neutral pH : enolisation 1,2 favored
O
HO H
H OH
H OH
NHR
HO
1,2- enolisationOH
HO H
H OH
H OH
NHR
HO
H+
H2O
OH
H
H OH
H OH
NR
HO
H2O
RNH3+
OH
H
H OH
H OH
O
HO
O
H
H OH
H OH
O
HO
H+
H2O
O
H
H OH
O
HO
H
H+
H2O
OCHO
OH
5-hydroxymethyl-2-furaldehyde
instable 3-desoxyhexulose
OH
H
HO
H
HO
NHOH
H
OH
R'
Machiels, D.; Istasse, L. Ann. Med. Chem. 2002, 146, 347-352.
II. Characteristic compounds: formation
2.2 Higher pH : 2,3 enolisation
Exemple: furaneol synthesis (strawberry, ananas, caramel)
enolisation 2,3
-RNH2
H OH
H OH
HO H
HO H
Me
H OH
H OH
HO H
HO H
Me
O
H OH
HO H
HO H
Me
OH
OH
HO H
HO H
Me
OH
OH
HO
HO H
Me
OH
+ RNH2
- H2O
NH
RRHN RHN
Amadori Rearrangement
Isomerisation
O
OH
O
HO
O
OHO
HOO
HOO
furaneol
- H2O
1-desoxyhexulose
-H+
Lizzani-Cuvelier L. et al. L’Act. Chim. 2002, 04, 4-14.
II. Characteristic compounds: formation
At « high » pH apparition of nitrogenous heteroaromatic rings.
Reductones so obtained can condensate with amino ketones to give after dehydratation different kind of pyrroles:
O
HHO
OHH
OHH
CH2OH
NHR
O
CH2
OHH
OHH
CH2OH
O
+
NR
O
H
OH
OH
HO
HOOHHO
dehydratation
condensation
…
II. Characteristic compounds: formation
3. Strecker degradation :
Reductones and dehydroreductones can undergo Strecker degradation by reacting with amino acid
Me
O
O
H OH
H OH
OH
+ H2N R
COOH
Me
O
N
H OH
H OH
OH
OH
O
R
H2O CO2
Me
OH
N
H OH
H OH
OH
R
H2O
Me
OH
NH2
H OH
H OH
OH
+R
O
H
Me
O
NH2
H OH
H OH
OH
Aminoketone
decarboxylation
hydrolysis
important intermediary
reductonefrom enolisation
pathways
II. Characteristic compounds: formation
Aminoketones can condensate and give heteroaromatics or react with another amino acid to give colored compound.
H2N
ONH2
O
OH
N
N
OH
N
N
N
Nrearomatisation- H2Odouble
condensation
2-methylpyrazine
R2
NH2
R1
OR2
NH2
R1
OH R3CHOR1
OH
R2
N
CHR3
O
HNR2
R1
R3O
NR2
R1
R3
[O]
Oxazoles
Bristow, M.; Isaacs, N. S. J. Chem. Soc., Perkin Trans. 2, 1999, 2213-2218
Lizzani-Cuvelier L. et al. L’Act. Chim. 2002, 04, 4-14.
II. Characteristic compounds: formation
Particular amino acids:
N
NH
COOH
O
R
N
N
O
N
N
N
N
O
Protein-bound tryptophane hardly reactive
Occur also in free state :
Ledl, F.; Schleicher, E. Angew. Chem. Int. Ed. 1990, 29, 565-706.
No Amadori rearrangement observed if N-glycosyl derivative
In the case of over-cooked products: formation of carcinogenic product N
NNH2
H2N COOH
NH
Tryptophane
Particular amino acids:
NH
COOH
Proline
Ledl, F.; Schleicher, E. Angew. Chem. Int. Ed. 1990, 29, 565-706.
Occurs in large amount in cereals, particularly in malt.
Lead to tastefull molecules
HNHOOC
O
ONHOOC
O
N
OH
ON
O
Heteroatome addition
Loss ofproton
N
O
Nucleophilicaddition
NO
H
NH
O
OH
opening of the dihydropyrrylium
ring followed by intra or
intermolecular condensation
Particular amino acids:
Do not occur free in food stuff
Release hydrogene sulfide
Low odor threshold (roasted coffee beans…)
Retarding effect on the reaction
H2N COOH
HS
Cysteine
HOOC
NH2
SS
NH2
COOH
Ledl, F.; Schleicher, E. Angew. Chem. Int. Ed. 1990, 29, 565-706.
S S
S
S
NH
SO O
SH SS
OS
N
Particular amino acids:
No reaction with guanido group
Trapping of carbonylated compounds
Cross linking to form colored compounds.
N NH
NNH
COOHH2N
NH2
COOH
NH
HNO
NH N N
NH
Ledl, F.; Schleicher, E. Angew. Chem. Int. Ed. 1990, 29, 565-706.
H2N COOH
HN
H2N NH
Arginine
HN COOH
NHRHN
Creatine
Arg-pyrimidine
Step which gives the taste and the color to the beer = roasting of the malt.
Main parameters : time, temperature and humidity rate during the roasting
HO
OH
O
OH
OH
OHO
OH
O
HO
HO
Maltose
HO
O
H
O
OO O
OH
O
H2N NHHN
COOHH2N
Argininefragmentation
- 2 H2O
N N
OH
HN
COOHH2N
- HCOOH
Glomb et al. J. Agric. Food Chem., 2001, 49, 366-372
Arg-pyrimidine
EBC: European Brewery ConventionBarley, water mixture
Filled circles = darker beers
Color not only depending of Arg-pyrimidine
For the same wort the darker beers have got a higher
content of Arg-pyrimidine
III. POLYMERISATION:
MELANOIDIN FORMATION
III. Polymerisation: Melanoidin formation
Polymerisation: Melanoidin formation
Give to the meat hardness and color…
No structure found to date…
Mix of polymers of different molecular weights
Made by polymerisation of different heterocycles thanks to retroaldolisation products…
Formation delayed by addition of water
enhanced by transition metal (Fe2+, Cu2+)
NH
H2N NH
H2N COOH
HN
NH2HN
NH2HOOC
N
NH2N
N
R'
NH2
COOH
N
N
O
R
COOHH2N
Scission productsStrecker degradation
aldehydes
H2N COOH
H2N
H2N COOH
H2NN N
H
NNH
COOHH2N
NH2
COOH
R1
O
R2
O
linking molecules
Maillard Reaction : in vivo…
Evidence of the first products of Maillard reaction found in vivo
Diabete:
N-term of hemoglobin can be glycosilated = Marker of diabetic people (2-3 months)
Other proteins can give shorter markers (2-3 weeks) or longer (hair’s or nails proteins)
Severe complications = high degree fructolysation increased damage to eyes and kidney
Aging:
Maillard products accumulate in the organisme
Link between aging damages and Maillard reaction… (collagen)
Ledl, F.; Schleicher, E. Angew. Chem. Int. Ed. 1990, 29, 565-706.
Control of Maillard reaction to preserve food and body
1. Kinetics:
Glucose + amino acids at 2°C : two months to have light yellow coloration
2. Additives:
Addition of sulfites : use strickly control specially because of their bad effects on asthmatic people
Structure identified after sulfite addition :
3. In vivo:
Administration of aminoguanidine :
Relatively well tolered by mammals
Lowered concentration of cross-linking of collagen and deposition of cholesterol transporting lipoproteins on the arterial walls.
CHO
O
CH2
SO3HH
OHH
CH2OH
OH
O
H
O
OH
H2C
O
OHH
OHH
CH2OH
NHR
HHH2N
HN
NH
NH2
+
H2C
N
OHH
OHH
CH2OH
NHR
HHNH
NH
NH2O
O H2N
HN
NH
NH2
+ N N
N
NH2
APPLICATION :
HETEROCYCLE SYNTHESIS
Pop corn like odorant…
De Kimpe, N. G., Rochetti, M. T. J. Agric. Food Chem., 1998, 46, 2278-2281
H2NSH
O
O
~1%
145°C, 20 min
+
NH
S
O
5-acetyl-2,3-dihydro-1,4-thiazine
SH
COOHH2N
O
H
HO
H
HO
H
OHOHH
H
OH
+
O
OH2SO4 (cat.)
50°C, 4h60%
OMeOMe
O
OMeOMe
N
OMeOMe
N
Br
iPrNH2, Et2O3 eqCH(OMe)3
NBS, CCl4,, 4h
99%TiCl4, 0.6 eq0°, RT, 2.5h
89%
OMeOMe
O
Br
(COOH)2.2H2OEt2O, , 1h
87%
HS
H2N
HClCH3CN, 3h
56%
Better yields are otained by running the last reaction in DCM with the N-Boc protected derivative of the thio coumpound.
Analogue synthesis
Azéma, L.; Bringaud, F.; Blonski, C.; Périé, J. Bioorg. Med. Chem. 2000, 8, 717-722.
THT1 glucose transporter of parasite causing African sleeping sickness also accepts D-fructose.
OHO
HOOH
OH
OH
H2N
H2O, AcOH
HO
OH
OH
OH
OH2, Pd/BaSO4
H2O, AcOHHO
OH
OH
OH
OHN NH3
HO
OH
OH
OH
OHN
S
O
O
N
DOWEX 1X8 (OH- form)dansyl chlorIde, MeOH
37%
Fluorescent fructose analogue
CH3COOD-glucose
Applications
Fernandez-Bolaños, J. G. et al. Tetrahedron Ass.. 2000, 14, 1009-1018.Yeagley, D. A.; Benesi, A. J., Miljkovic, M. Carbohydr. Res. 1996, 289, 189-191.
Horvat, S. et al. J. Chem. Soc., Perkin Trans.1 1998, 909-913.
O
O
AcOOAc
OAc
ONBS, CCl4, reflux
O
O
AcOOAc
OAc
Br
O
Ph AcSK, DMSO, rtO
OBz
AcOOAc
OAc
SAc
H2O2, AcOH, KOAc40°C, 16h
O
OBz
AcOOAc
OAc
SO3K1. NaOMe, MeOH, RT2. Amberlite IR-120 (H+)3. aq. KOH (1eq)O
OH
HOOH
OH
SO3K
OH
CH2NH2RO
OHOH
SO3
RNH2
-H2O
94%precursor of a
DNA polymerase inhibitor
72% over 2 steps
90% over 4 steps
Ph
OHO
HOOH
O
OH
Leu-Phe-Gly-Gly-Tyr-H
O
OH
Tyr
HO OH
OO
Leu
OPhe Gly
Gly
dry pyridine:AcOH24h, rt
58%
hydrolysis0.1M NH4OH
55%
OHO
HOOH
OH
Tyr-Gly-Gly-Phe-Leu
Application piperidinone
Guzi, T. J.; Macdonald, T.L. Tetrahedron Lett. 1996, 17, 2939-2942
NO COOMe
OMeMeO
OBn
NO
OMeMeO
OBn
O
O
Application piperidinone synthesis
HONH2
phtalic anhydridetoluene, reflux
73% HON
O
OSwern oxidation
89% ON
O
OH
MeOOBn
OMe
N CNO
LDATHF:HMPA
-78°C
82%
N
O
OOH
N
CN
O
OMe
MeO
BnO1. N2H42. ClCOOMeTEA, DCM
70%
HN
O
OH
N
CN
O
OMe
MeO
BnO
OMe
HN
O
OH
OMe
MeO
BnO
OMe
O
AcOH 70%
77%
pTsOH, toluene, reflux
82%
NO COOMe
OMeMeO
OBn
Guzi, T. J.; Macdonald, T.L. Tetrahedron Lett. 1996, 17, 2939-2942
Application piperidinone synthesis
Guzi, T. J.; Macdonald T. L. Tetrahedron Lett. 1996, 17, 2939-2942
BnO BrBuLi, THF, -78°C
85%
1. 10% HCl ; 92%2. NaBH4 ; 80%
MeOOBn
OMe
N CNO
AcOH 70%
80%
N
N
OEt
OEt
N
N
OEt
OEt
BnONH2
BnO OH
1. (EtO)2CO, NaOEt 91%2. (Boc)2O, DMAP, TEA 89%
BocN
BnOO
O
1. H2, 10% Pd/C 95%2. Swern Oxidation 86%
BocNO
O
O
KHMDS, THF, -78°C
64%
OH
N
CN
O
OMe
MeO
BnO
HNO
O
OH
OMe
MeO
BnO
HNO
O
O
pTsOHtoluene, reflux
85%
NO
OMeMeO
OBn
O
O
Conclusion
Maillard reaction lead to a huge amount of different compounds:
N
HO
HO
H
O
H
O
NO
N
HO H
O
N
N
O
O
N
OH
O
O
O
NH
O
N
N
O
H H
O
OHH
O
H
O
H
O
O
OH
H
O
O
OH
O
HO
HO
O
H
O
O
O
OH
O
O HO
OH
OH
O
H
OCHO
OHNR
O
H
O
NR2
R1
R3
N
NH
COOH
O
R
N
N
O
S
N
N N
OH
HN
COOHH2N
N
NH2N
N
R'
NH2
COOH
N
N
O
R
COOHH2N
NH
S
O
NO COOMe
OMeMeO
OBn
O
O
OH
Molecular Gastronomy
Hervé ThisNicholas Kurti
Ferran Adria,
Heston Blummenthal,
Pierre Gagnaire,
Emile Jung,
Bernard Leprince,
Michel Roth,
Pierre Hermé…
Molecular Gastronomy
First target : eggs and mayonnaise
Scientifical optimisation of the emulsion quality1 litre of mayonnaise from 1 yolk !Verification of advice
When eggs are overcooked: apparition of gray-green layer around the yolk.
Iron from yolk and sulfure from white lead to FeS2 which give bad taste and color.
Molecular Gastronomy
KBH4
Molecular Gastronomy
This, H. Nature Materials, 2005, 4, 5-7
During the cooking, Mg2+ of chlorophyll are replaced by 2 H+
Solution : baking soda in the cooking water….
« Pour the peas in cold water to fix the chlorophyll… »
Molecular Gastronomy
This, H. Nature Materials, 2005, 4, 5-7.
Raspberries crushed with Sn2+
Complexation with polyphenols
Raspberries crushed in water
« Red berries should not be cooked in tin or copper pan... »
O
OH
HO
O
OH
OH
OH
quercetine
Molecular Gastronomy
Cheap Tips….
Whisky few drops of vaniline :
ethanol + lignin of wood barrels give 4-hydroxy-3-methoxybenzaldehyde
No Mushrooms ?
Use an appropriate amount of 1-octen-2-ol or benzyl trans-2-methylbutenoate
OO
HO
O
O
OH
Molecular Gastronomy
Märkl, G. Angew. Chem. Int. Ed. 2003, 42, 5386-5388.
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