Fischer Projectionrepresentation of a 3D molecule as a flat structure where a tetrahedral carbon is represented as two crossedlines.

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Fischer Projection

representation of a 3D molecule as a flat structure where a tetrahedral carbon is represented as two crossed lines.

C

carbon substituent

horizonal line is coming out of the plane of the page

vertical line is going back behind of the plane of the page

HOH2C CHO H OH (R)-(+)-glyceraldehyde CHO CH2OH OH H CHO CH2OH OH H Fischer projection

Manipulation of Fischer Projections:

1. Fischer Projection can be rotated by 180 ° only!

(R)-(+)-glyceraldehyde CHO CH2OH OH H CH₂OH CHO H HO 180 ° rotation still (R)-(+)-glyceraldehyde

Rotation by 90 ° or -90 ° (270 °) invert the stereochemistry

(R)-(+)-glyceraldehyde CHO CH2OH OH H 90 ° rotation H OH CHO HOH₂C CHO CH2OH OH H H OH CHO HOH2C (S)-(-)-glyceraldehyde

These two compounds are enantiomers

Because of the convention of the Fischer Projection (i.e., the vertical lines are going back and the horizonal lines are coming forward) the 90° rotated Fisher projection is actually the enantiomer of the original

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2. If one group of the Fischer projection is held steady, the other groups can be rotated either clockwise or counter clockwise.

(R)-(+)-glyceraldehyde _{(R)-(+)-glyceraldehyde}still CHO

CH2OH

OH H

hold this group steady

CHO

OH H HOH₂C

Assigning R and S-configurations to Fischer projections

1. Assign priorities to the four substituents according to the Cahn-Ingold-Prelog convention.

2. Perform the two allowed manipulations of the Fischer projection to place the lowest priority group on one of the vertical positions (either top or bottom)

3. If the priorities of the other three groups (1-2-3) proceed clockwise, the stereogenic center is assigned as R. If the priorities of the other three groups (1-2-3) proceed counter clockwise, the stereogenic center is assigned as S. CHO CH₂OH OH H 1 2 3 4 lowest priority group. Move to a vertical position H CH₂OH CHO HO 1 3 4 2 hold one group

steady and rotate the other three

The priorities of the other three groups (1-2-3) is clockwise. The stereogenic center is assign as R hold

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For more structures with more than one stereogenic center such as carbohydrates, the tetrahedral carbons are "stacked" on top of one another.

H HO O HO OH Threose CHO H OH HO CH₂OH H

For carbohydrates, the convention is to put the carbonyl group at the top for aldoses and closest to the top for ketoses. The carbons are numbered from top to bottom.

H CHO OH H HO OH H OH H CH₂OH CH2OH O H HO OH H OH H CH₂OH D-Glucose D-Fructose 1 ₁ 2

Carbohydrates and amino acids are designated as D- or L- according to the stereochemistry of the highest numbered carbon in the Fischer projection. If the hydroxyl group (or amino group for amino acids) is pointing to the right in the Fischer Projection, the sugar (or amino acid) is designated as D. If the

hydroxyl group (or amino group for amino acids) is pointing to the left in the Fischer projection, the sugar (or amino acid) is designated as L. Most naturally occurring carbohydrates are of the D-configuration while most naturally occurring amino acids are L.

H CHO OH H HO OH H OH H CH₂OH D-Glucose 1 CHO OH H H HO H HO CH2OH L-Arabinose 1 highest numbered stereogenic carbon highest numbered stereogenic carbon 2 3 4 5 6 4 5 3 2

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Converting Fischer Projections into Haworth Projections.

1. Identify the hydroxyl group which is cyclizing onto the carbonyl group. This hydroxy will become the ring oxygen in the hemiacetal or hemiketal form of the carbohydrate. For D-glucose, it is the C5 hydroxyl in the pyranose form; for D-ribose, it is the C4-hydroxyl for the furanose form.

2. Manipulate the Fischer projection so this hydroxyl group is on the bottom.

3. Draw the Haworth projection so that the ring oxygen is on the top. For pyranoses, draw the six-membered ring laying on it side with a oxygen at the upper right.

4. Substituents on the right side of the Fischer projection will be on the bottom face of the Haworth projection. Substituents on the left side of the Fischer projection will be on the top face of the Haworth projection.

5. Remember that in the cyclic form, the C1-hydroxyl group (the anomeric center) can usually adopt either the up or down configuration.

H CHO OH H HO OH H OH H CH2OH H CHO OH H HO OH H H HOH₂C OH

D-glucose

Ring oxygen T O B T B T B B T T B T B T B B B T T O Pyranose Furanose T= top B= bottom O OH OH CH2OH OH OH 1 1 2 3 4 5 6 β-D-glucopyranose CHO OH H OH H OH H CH2OH CHO OH H OH H H HOH₂C OH

D-Ribose

Ring oxygen 1 OH OH OH O HO β-D-ribofuranose 1 2 3 4 6