To name the enantiomers of a compound unambiguously, their names must include the "handedness" of the molecule. The method that has been developed to do this is formally known as R,S nomenclature.
The method of unambiguously assgning the handiness of molecules was originated by three chemists: R.S. Cahn, C. Ingold, and V. Prelog and, as such, is also often called the Cahn-Ingold-Prelog rules. In addition to the Cahn ingold system, there are two ways of experimentally determining an enantiomer's absolute configuration:
However, for non-lab purposes, it is beneficial to focus on the R-S system. The sign of optical rotation, although different for the two enantiomers of a chiral molecule,at the same temperature, cannot be used to establish the absolute configuration of an enantiomer. This is because the sign of optical rotation for a particular enantiomer may change when the temperature changes.
The "right hand" and "left hand" nomenclature is used to name the enantiomers of a chiral compound. The stereocenters are labeled as R or S.
Look at the first picture, then draw a curved arrow from the highest priority (1) substituent to the lowest priority (4) substituent. If the arrow goes in a counterclockwise direction (left when leaving the 12'o clock position), the configuration at stereocenter is considered S ("Sinister" → Latin= "left"). If, however, the arrow turns clockwise,(Right when leaving the 12'o clock position) then the stereocenter is labeled R ("Rectus" → Latin= "right").
The R or S is then added as a prefix ,in parenthesis, to the name of the specific enantiomer we are concerned about.
Before you can apply the R and S nomenclature to a stereocenter, you have to prioritize your substituents. Follow these rules to prioritize:
First look at the atoms that are directly attached to the stereocenter of the compound. A substituent that has a higher atomic number takes precedence over a substituent that has a lower atomic number. Hydrogen is the lowest possible priority substituent, because it has the lowest atomic number.
When looking at a problem with wedges and dashes: if the lowest priority atom is not on the dashed line going away from you, you must rotate the molecules so that the lowest priority bond is facing away from you.
When you have two substituents with equal rank, you must proceed along the two substituent chains until you find a point of difference.
First, you determine which of the chains has the first connection to an atom with the highest priority-the highest atomic number. That chain will have the higher priority.
If the chains are similar keep going down the chain, until you can find a point of difference.
For example: an ethyl substituent will take priority over a methyl substituent. At the connectivity of the stereocenter, both have a Carbon, which are equal in rank. Going down the chains, a methyl has only has Hydrogen atoms attached to it while the ethyl has another Carbon attached to it. The Carbon on the ethyl is the first point of difference and has a bigger atomic number than Hydrogen:therefore the ethyl takes priority over the methyl.
If a chain is connected to the same kind of atom twice or three times. Check to see if the atom it is connected to has a greater atomic number than any of the atoms that the competing chain is connected to.
|A 1-Methylethyl substituent will take precedence over an Ethyl substituent. Connected to the first carbon, ethyl only has one other Carbon whereas the 1-Methylethyl has two Carbons attached to the first Carbon; this is the first point of difference. Therefore, 1-Methylethyl will rank higher in priority than Ethyl, as shown below: |
Remember that being double or triple bonded to an atom means that the atom is connected to the same atom twice. And in such a case you would follow the same method as above.
After all your substituents have been prioritized in the correct manner, you can now name/label the molecule R or S.
i) If it is clockwise it is R
USE YOUR MODELING KIT: Making models will help you visualize the structure. When you make a model, make sure the lowest priority is pointing away from you. Then determine what direction you have to go from the highest priority substituent to the lowest: Clockwise (R) or Counterclockwise(S).
IF YOU DO NOT HAVE A MODELING KIT: remember that the dashes mean the bond is going into the screen and the wedges means that bond is coming out of the screen. If your lowest priority bond is not pointing to the back, mentally rotate it so that it is. However, it would help you greatly when learning organic chemistry to get one.
If you have a modeling kit use it to help you solve the following practice problems.
Are the following R or S?
I > Br > F > H. The lowest priority substituent, H, is already going towards the back. It turns left going from I to Br to F, so it's a S.
Br > Cl > CH3 > H. You have to switch the H and Br in order to place the H, the lowest priority, in the back. Then, going from Br to Cl, CH3 is turning to the right, giving you a R.
(3) Neither R or S
This molecule is achiral. Only chiral molecules can be named R or S.
OH > CN > CH2NH2 > H. The H, the lowest priority, has to be switched to the back. Then, going from OH to CN to CH2NH2, you are turning right, giving you a R.
COOH > C triple bond CH > HOH2C > H. You have to switch H with COOH so that H is going towards the back. Then, going from COOH to C triple bond CH to HOH2C, you are turning left, giving you a S.
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