Organic Chemistry — Stereochemistry: Determine Stereocenter Configuration R or S

Question 

For the following compounds, assign R or S configurations for each stereocenter. 

  1. Bromine, oxygen, and carbon compound. Bromine is on top, oxygen is bottom left, and carbon is bottom right.
    Compound A
  2. Carbon, fluorine, and iodine compound. Carbon is on top, fluorine is bottom left, and iodine is bottom right.
    Compound B
  3. Carbon, iodine, and oxygen compound. Carbon is on top, iodine is bottom right, and oxygen is bottom left.
    Compound C

 

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  1. S
  2. R
  3. R

Refer to Section 8.4: Absolute Configuration- R-S Sequence Rules (1).

Strategy Map

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Table 1: Strategy Map
Strategy Map Steps
1. Identify chiral carbon with four different groups attached
2. Assign priorities to substituents and label them one through four.

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Refer to Section 8.4: Absolute Configuration- R-S Sequence Rules (1).

3. Rotate the molecule so that the lowest priority group (#4) is facing away from you (towards the back)
4. Count in the direction of 1 to 3 and identify if this is clockwise or counterclockwise.

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Clockwise = R
Counterclockwise = S

Solution

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a. Compound A

  • S
  • Priority goes counterclockwise around the stereocenter.

b. Compound B

  • R
  • Priority goes clockwise around the stereocenter.

c. Compound C

  • R
  • The hydrogen (not shown in the line-dash-wedge structure) is wedged towards the viewer; therefore, the chirality will be the opposite.
  • Priority goes counterclockwise (S) around the stereocenter as drawn; therefore, the chiral center is R.

 

Guided Solution

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The guided solution below will give you the reasoning for each step to get your answer, with reminders and hints.

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Table 2: Guided Solution
Guided Solution Ideas
This question is a theory problem where you assign the correct configuration to a carbon stereocenter (R or S).

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Refer to Section 8.4: Absolute Configuration- R-S Sequence Rules (1).

For the following compounds, assign R or S configurations for each stereocenter.

  1. Bromine, oxygen, and carbon compound. Bromine is on top, oxygen is bottom left, and carbon is bottom right.
    Compound A
  2. Carbon, fluorine, and iodine compound. Carbon is on top, fluorine is bottom left, and iodine is bottom right.
    Compound B
  3. Carbon, iodine, and oxygen compound. Carbon is on top, iodine is bottom right, and oxygen is bottom left.
    Compound C
The rules to assign priority to substituents:

  1. First, examine the atoms directly attached to the stereocenter of the compound. An atom with a higher atomic number takes precedence over an atom with a lower number. Hydrogen is the lowest possible priority atom because it has the lowest atomic number.
    1. Ensure that the lowest priority group is pointed away (dashed back)
  2. If two or more substituents have the same element directly attached to chiral carbon, proceed along the substituent chains until you find a point of difference. Determine which chain has the first connection to an atom with the highest priority (the highest atomic number). That chain has the higher priority.
  3. For assigning priority, treat multiple bonds as if each bond of the multiple bond is bonded to a unique atom. For example, an alkene substituent (CH2=CH-) has a higher priority than an ethyl substituent (CH3CH2-).
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Refer to Section 8.4: Absolute Configuration- R-S Sequence Rules (1).

R vs S configuration

To identify the configuration of a stereocenter, you must identify if your order of priority goes in the clockwise or counterclockwise direction.

Clockwise = R
Counterclockwise = S

Table 3: Complete Solution
Complete Solution
a. Compound A

Bromine, oxygen, and carbon compound. Bromine is on top, oxygen is bottom left, and carbon is bottom right.
Compound A

Bromine is the first priority (atomic number 35).
Oxygen is the second priority (atomic number 8).
Carbon is the third priority (atomic number 6).

It goes counterclockwise around the stereocenter.

Answer: S

b. Compound B

Carbon, fluorine, and iodine compound. Carbon is on top, fluorine is bottom left, and iodine is bottom right.
Compound B

Iodine is the first priority (atomic number 53).
Fluorine is the second priority (atomic number 9).
Carbon is the third priority (atomic number 6).

It goes clockwise around the stereocenter.

Answer: R

c. Compound C

Carbon, iodine, and oxygen compound. Carbon is on top, iodine is bottom right, and oxygen is bottom left.
Compound C

Hydrogen is wedged forward, so you must rotate the molecule or reverse the stereochemistry determined, as drawn below.

Compound C rotated so oxygen is bottom left (with H furthest from center) and iodine is bottom right.
Rotated Compound C

Hydrogen, the lowest priority group, is now dashed back.
Iodine is the first priority (atomic number 53).
Oxygen is the second priority (atomic number 8).
Carbon is the third priority (atomic number 6).

It goes counterclockwise around the stereocenter in the original figure.
It goes clockwise in the rotated molecule.

Answer: R

Check Your Work

Check to make sure you are following the guidelines of labelling priority. Ensure you go atom by atom.

Does your answer make chemical sense? 

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We use the “right hand” and “left hand” nomenclature to name the enantiomers of a chiral compound. We label the stereocenters as (R) or (S).

These naming rules provide an unambiguous name that indicates the molecule’s stereochemistry.

PASS Attribution

Media Attributions

References

1. LibreTexts. 8.4: Absolute Configuration- R-S Sequence Rules. In CHEM1500: Chemical Bonding and Organic Chemistry. LibreTexts, 2022. https://chem.libretexts.org/Courses/Thompson_Rivers_University/CHEM1500%3A_Chemical_Bonding_and_Organic_Chemistry/08%3A_Organic_Chemistry_II_-_Stereochemistry/8.04%3A_Absolute_Configuration-_R-S__Sequence_Rules.

2. Blackstock, L.; Brewer, S.; Jensen, A. 8.2. Question 8.4.E.1 PASS – Stereocenter Configuration R or S. In PASS Chemistry Book CHEM 1500. LibreTexts, 2024. https://chem.libretexts.org/Courses/Thompson_Rivers_University/PASS_Chemistry_Book_CHEM_1500/08%3A_Organic_Chemistry_II_-_Stereochemistry/8.2._Question_8.4.E.1_PASS_-_stereocenter_configuration_R_or_S.

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