1 Amine- Amine -containing Natural Products containing Natural - - PDF document

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Biological Chemistry Biological Chemistry

• Amines
• Functional group summary
• Carbohydrate structure
• Lipid structure
• Amino acid structure
• Nucleic acid structure

Amines: Amines: Nucleophiles Nucleophiles and Bases and Bases

Structure – N is sp3 hybridized, H-N-H bond angles in CH3NH2 ~ 106o Alkyl substituents cause larger bond angles due to steric hindrance

A ball-and-stick model

• f methylamine

Figure 22.1

Amines as Bases Amines as Bases

Amine bases stronger than H2O or ROH but much weaker than HO- or RO-

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Amine Amine-

• containing Natural Products

containing Natural Products

HO O HO H N morphine O O HO H N codeine OH N H O N quinine HO OH NH HO epinephrine H2N NH2 cadaverine H2N NH2 putrescine N N nicotine

Amino Acids Amino Acids – – Building Blocks for Proteins Building Blocks for Proteins Functional Group Summary Functional Group Summary

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Functional Group Summary Functional Group Summary

Functional Group Summary Functional Group Summary

OCH3

NH2

Cl

O

O O O O O

OH

NH2 O HO OH H3CO OCH3

Functional Group Summary Functional Group Summary

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Carbohydrate Structure Carbohydrate Structure

All present in solution, free sugars can interconvert Furanose forms Pyranose forms

Carbohydrate Structure Carbohydrate Structure

D-glucose D-galactose D-glucosamine D-GlcNAc L-Fucose D-ManAcA D-Ribose 2-Deoxy-D-ribose

Carbohydrate Structure Carbohydrate Structure -

• Mutarotation

Mutarotation

• dissolve dextrose in water, measure [α]D : +112.2
• dissolve β-D-glucopyranose in water, measure [α]D : +18.7
• allow either to equilibrate, measure [α]D : +52.5

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• Free sugar + alcohol + acid gives a glycoside
• Glycosides are no longer free sugars and do not mutarotate

Carbohydrate Structure Carbohydrate Structure -

• Glycosides

Glycosides Carbohydrate Structure Carbohydrate Structure – – Glycosides; Disaccharides Glycosides; Disaccharides

Note: 2 amino acids give 4 peptides; 2 hexoses can give >20 possible reducing disaccharides

Carbohydrate Structure Carbohydrate Structure – – Glycosides; Oligosaccharides Glycosides; Oligosaccharides

Blood antigens

H (type O) A (type A) B (type B)

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Carbohydrate Structure Carbohydrate Structure – – Biological Recognition Biological Recognition

Molecular recognition

• multiple functional groups
• multiple contact points
• more complex alphabet than peptides

Important Functions

• cell-cell adhesion
• antibody recognition
• viral and bacterial adhesion

Carbohydrate Structure Carbohydrate Structure – – Glycosides; Vaccines Glycosides; Vaccines

Danishefsky et. al. Sloan-Kettering/Columbia – Synthetic vaccine against 3 types of cancer

Lipid Structure Lipid Structure

An unsaturated fat (triglyceride) A saturated fat (triglyceride)

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Lipid Biosynthesis Lipid Biosynthesis

Acetyl coenzyme A can serve as a 2-carbon nucleophile or electrophile as needed

Lipid Biosynthesis Lipid Biosynthesis

carbon chain extended by 2, can go up to C16, C18, C20 iteratively

Lipid Structures Lipid Structures

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Lipid Structures Lipid Structures – – Prostaglandins Prostaglandins

OH Vitamin A

• Carotone

OPP OPP dimethylallyl pyrophosphate isopentyl pyrophosphate OPP (-H+) Geranyl pyrophosphate

Terpene Terpene Biosynthesis Biosynthesis Biosynthetic Pathways Biosynthetic Pathways

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Transfer of Information in Protein Expression Transfer of Information in Protein Expression

mRNA Protein

Double-stranded DNA transcription translation Amino Acids and Nucleic Acids Amino Acids and Nucleic Acids

X-ray crystal structure of peanut lectin bound to C-lactose (Kishi et. al.)

Amino Acids Amino Acids-

• Structures

Structures

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Amino Acids and Peptide Linkages Amino Acids and Peptide Linkages Amino Acids and Peptide Linkages Amino Acids and Peptide Linkages

polypeptide

Amino Acids and Peptide Linkages Amino Acids and Peptide Linkages

Organic Chem Biochemistry Structural Biology

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Ribbons and coils represent amino acid sequences in α-helical or β-sheet arrangements

Amino Acids and Proteins Amino Acids and Proteins – – 3 3o

• and 4

and 4o

• Structure

Structure Protein Function, e.g. Catalysis (Enzymes) Protein Function, e.g. Catalysis (Enzymes)

O HO HO OH O OH CN O HO HO OH HO OH CN OH glycosidase

Structure 1995, 3, 951-960 Cyanogenic β-Glucosidase from White Clover

Transfer of Information in Protein Expression Transfer of Information in Protein Expression

mRNA Protein

Double-stranded DNA transcription translation

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Nucleic Acid Structure Nucleic Acid Structure – – Genetic Alphabet Genetic Alphabet

N N N N NH2 O H OH HO adenosine guanosine NH N N O NH2 N O H OH HO cytidine O H OH HO N N NH2 O thymidine O H OH HO N NH O O

Nucleic Acid Structure Nucleic Acid Structure – – DNA Alphabet DNA Alphabet Nucleic Acid Structure Nucleic Acid Structure – – RNA Alphabet RNA Alphabet

N N N N NH2 O H OH HO adenosine guanosine NH N N O NH2 N O H OH HO cytidine O H OH HO N N NH2 O uridine O H OH HO N NH O O

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Nucleic Acid Structure Nucleic Acid Structure – – Phosphate Derivatives Phosphate Derivatives Nucleic Acid Structure Nucleic Acid Structure – – RNA and DNA Polymers RNA and DNA Polymers RNA and DNA Polymers RNA and DNA Polymers – – Hydrogen Hydrogen-

• bonding Interactions

bonding Interactions

2 H bonds hold A and T together 3 H bonds hold G and C together

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RNA and DNA Polymers RNA and DNA Polymers – – Information Storage Information Storage Biological Communication and Construction Biological Communication and Construction

Organic material

biosynthesis

Biological Systems

1800 – Organic Chemistry : the chemistry of natural products based on carbon 2008 – Organic Chemistry : “molecular engineering”

H C H H H

Chem Chem 3719/3720 3719/3720 – – Introduction to Organic Chemistry Introduction to Organic Chemistry