CHEM237 2013F Unni, 09/19/13 Understanding Fischer Projections Fischer projections are useful ways to represent compounds with

one or more chiral centers. You must understand and do the following: 1. Assign absolute configuration at each chiral center. 2. Identify line-bond and Fischer projections as identical, enantiomers, diastereomers, or none of these. 3. Convert structures between perspective drawings and Fischer projections. Here are some examples to explain how this can be done and can be applied as a general technique.
Br Cl CH3 H H CH3 A Br H CH3 H Cl CH3 B H Br CH3 Cl CH3 H C H Cl Br D H

1. Assign absolute configuration at each chiral center. As mentioned in class, use the clockwise and counterclockwise rotation of the 1-4 CIP assigned groups. First, remember that vertical lines in the Fischer projections are going back into the page and horizontal are coming out. And, drawing a Fischer projection from a perspective drawing requires them to correctly vertical and horizontal as well.
CH3 Br H Cl H CH3 A CH3 Br H Cl H CH3 1 Br Cl 1 3 CH3 4 order in CW 22 H or CCW for H 4 1-3. CH3 3 CCW = S, but H is horizontal, so its R CW = R, but H is horizontal, so its S CH3 H H (S) CH3
(R)

Identify chiral centers, assign priorities

Br Cl

A (2R,3S)-2-bromo3-chlorobutane

2. Identify line-bond and Fischer projections as identical, enantiomers, diastereomers, or none of these. There are several ways to do this; redraw the structures so they are the same (or not), or assign the absolute configuration. Both can lead to errors if done incorrectly and the latter is less likely to go wrong, but sometimes a simple bond rotation can give the simple answer if the configuration is not needed. Take structures A and B below, and because they arent mirror images, they are not enantiomers. I have drawn the enantiomer of A (ent-A) with the mirror (dashed line) to show the difference. B and ent-A are different because the Br & H are swapped between the two structures, meaning they are not identical. Fortunately, we have already determined that structure A is 2R,3S. Structure B has the same spacial arrangement for the 2-carbon as it does in structure A when view from the same carbon numbering order, so it is also an R configuration (which you should confirm). Carbon 3 (Cl attached) in structure B has a pair of groups swapped (Cl & H) with respect to structure A, so that must mean it has been inverted, or the absolute configuration is opposite. We can check this, and it is verified, structure B is 2R,3R. If you are clever, you can see immediately that Bs carbon 3 is opposite to As, so Bs must be R because As is S.

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CHEM237 2013F Unni, 09/19/13 This is a very fast way of determining the configuration of similarly drawn (and prioritized!) molecules, but if you error on your original analysis, that will be propagated through the rest of your configurations, so be careful.
The Check! CH3 Br H Cl H CH3 A CH3 H Br H Cl CH3 ent-A
(R) CH3 Br 2 H Cl 1 4H CH3 3

CCW = S, but H is horizontal, so its R

(R)

Because B is not the opposite configuration of EACH center in structure A, structure B is not the enantiomer of structure A (as noted by the lack of mirror symmetry in drawing), but at least one center is opposite, so structures A and B are diastereomers of each other. Now consider structure C, which appears to be more complicated. Easily, we can see that the structure is very different because the 2-carbon (containing the Br) is drawn on the bottom. There are three options to solve it. First is to rotate the structure 180 so the 2-carbon is on top. This operation is okay, because horizontal bonds remain horizontal after the rotation, as do the vertical. (Remember 90 rotations are forbidden). Now the H on the 2-carbon is vertical so it looks different than either structures A or B. Although tempting, you cannot simply assign this center as S because the Br is on the right like it is in structure ent-A. Two groups were swapped, H and CH3, so it is not a direct comparison. Using the CIP analysis, it is an R configuration, and the other carbon is S. This is a 2R,3S, which identical to structure A and a diastereomer of structure B. The other option is that the 180 wasnt necessary, we could have just assigned the configurations, which also gives 2R,3S (be careful to assign the Br containing carbon as 2).
CH3 H Cl Br CH3 H C H (R) H3C Br Cl H (S) CH3 C flipped or just determine the configurations 3 CH 3 4 H Cl 1 22 Br CH3 1 H 3 4 C
(S) (R)

180 rotation

(2R,3S)

Another trick shown below is to hold a group and rotate the other three groups in either a CW or CCW direction, but making sure the carbon chain that was vertical doesnt get moved. A generic example is below, and all structures, X, Y, and Z are the same structures. The direction of rotation can be either CW or CCW, and it can be done more than once. This is a very effective method and can be applied to single chiral center projections where any group can be held with the others spun in a series of operations. (A majority of my previous students like this process, and it is not introduced in the book. I call it the hold and spin method).
b a f
C1
C2

c d

hold C2 group and spin a-b-c groups CW

a c f
C1
C2

b d

hold C1 group and spin d-e-f groups CW

a c d
C1
C2

b e

e X

e Y

f Z

3. Convert structures between line-bond and Fischer projections. Determining the absolute configurations of the two carbons in structure D is straight forward. This shows that structure D is 2S,3R which is the enantiomer of structure A. That might be simple, but converting it to the Fischer projection maybe isnt as easy for some people.

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CHEM237 2013F Unni, 09/19/13

H Cl H D Br determine configurations 2 3 Cl 2 1 H Br (S) 4 1
(R) (R) (S)

4 H

To convert the structure to a Fischer projection from the line-bond form, you start by rotating the C-C bond to make a backbone that is in one plane, preferably in the plane of the paper. Rotate to ensure the vertical bonds are going in the plane of the paper and the horizontal bonds are coming out of the page. Laying flat (creating a projection) shows the Fischer projection, again showing 2S,3R, then enantiomer of A. As the bottom example shows, it doesnt matter which atom is put verticle as long as the rotation is consistent with the original structure. The bottom structure is also 2S,3R, and a single hold (carbon 3) and spin of carbon 2 once CCW gives the same structure above it.
H Cl H Br rotate C-C bond H Cl Br Cl H H Br CH3 CH3 Cl (R) H CH3 H CH3 Br (S) H Br Cl (R) CH3 H (S) CH3

move Cl-C-C-Br in vertical plane

60 CW

alternatively,

180 rotation

H Cl

Br H

Cl move Cl-C-C-Me H CH3 in vertical plane Br H CH3

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