Learn · Organic Chemistry

R/S configuration: the CIP priority rules

How to assign R or S to a stereocenter using the Cahn–Ingold–Prelog priority rules, with the tricks for tied priorities.

Quick answer Rank the four groups 1 (highest) to 4 (lowest) by atomic number, then turn group 4 away and trace 1 → 2 → 3: clockwise is R, counterclockwise is S. If group 4 points toward you, read the rotation and flip it.

R and S label the two mirror-image arrangements — the handedness — of a stereocenter, using the Cahn–Ingold–Prelog (CIP) rules: rank four groups, read the rotation.

(R)-2-bromobutane
(S)-2-bromobutane

The two enantiomers of 2-bromobutane — same connectivity, mirror-image handedness, opposite CIP labels.

1. Assign a Priority (1–4) to the Four Groups by Atomic Number (CIP)

Rank the four directly bonded atoms by atomic number alone (Br > Cl > F > O > N > C > H); in 2-bromobutane Br is 1, H is 4, and the two carbons stay tied.

2-bromobutane: Br is #1, H is #4 by atomic number alone

2. Break Ties by Exploring Outward, Atom by Atom, to the First Point of Difference

When first atoms tie, compare the sets one bond out until they differ: ethyl's (C,H,H) beats methyl's (H,H,H), giving Br > CH₂CH₃ > CH₃ > H.

2-butanol: OH > CH₂CH₃ > CH₃ > H — ethyl (C,H,H) beats methyl (H,H,H)

3. Treat Every Double and Triple Bond as Duplicated Atoms

Each multiple bond adds a phantom duplicate atom, so a carboxyl carbon reads as (O,O,O) — outranking a CH₂OH carbon's (O,H,H), as in lactic acid.

Lactic acid: OH (1) > COOH carbon seen as (O,O,O) (2) > CH₃ (3) > H (4)

4. Orient the Molecule So the Lowest Priority (4) Points Away From You

Aim priority 4 into the page; when it already sits on a dashed bond — as with H in bromochlorofluoromethane (Br > Cl > F > H) — read the front three straight off.

Bromochlorofluoromethane: Br > Cl > F > H — put H in back and read the front three

5. Trace 1 → 2 → 3: Clockwise = R, Counterclockwise = S

With #4 away, a clockwise 1→2→3 sweep is R (rectus) and counterclockwise is S (sinister) — trace both glyceraldehyde enantiomers below.

(R)-glyceraldehyde — 1→2→3 clockwise
(S)-glyceraldehyde — 1→2→3 counterclockwise

6. If the Lowest Priority Points Toward You, Determine the Rotation and Flip It

When #4 is on a wedge, read the 1→2→3 rotation as drawn and reverse it — clockwise then becomes S, as in 1-bromo-1-chloroethane (Br > Cl > CH₃ > H).

1-bromo-1-chloroethane: Br > Cl > CH₃ > H — if H is on a wedge, read and flip

7. Remember: R/S Is Independent of (+)/(−) Optical Rotation

R/S is pure geometry; (+)/(−) is the measured direction of optical rotation, with no fixed link — (S)-alanine (NH₂ > COOH > CH₃ > H) happens to be natural L-alanine, a fact you memorize.

Alanine: NH₂ (1) > COOH (2) > CH₃ (3) > H (4) — this stereocenter is (S)

8. Summary

Rank by atomic number · break ties one bond out · count multiple bonds as duplicates · put #4 away · trace 1→2→3 (CW = R, CCW = S) · flip if #4 faces you · R/S ≠ (+)/(−).

Quiz yourself

Tap a question to reveal the answer — free, no login.

Both start with carbon, so it's a tie at the first atom. Exploring one bond out, the ethyl carbon is bonded to (C, H, H) while the methyl carbon is bonded to (H, H, H). C beats H at the first point of difference, so ethyl (CH₂CH₃) has higher priority than methyl (CH₃).

The double bond is treated as duplicated atoms. A carboxyl carbon (–COOH) is seen as bonded to (O, O, O) — the real –OH oxygen, the carbonyl oxygen, and a duplicate of that carbonyl oxygen. That's why –COOH outranks a –CH₂OH carbon, which is only bonded to (O, H, H).

S. The clockwise reading would mean R only if priority 4 pointed away. Because #4 points toward you, you flip the result — so a clockwise-as-drawn rotation is actually S.

No. R/S describes 3-D geometry from the CIP rules; (+)/(−) describes the measured direction of optical rotation. There is no fixed relationship between them — an (R) compound may be (+) or (−), and the sign must be determined experimentally, not deduced from the configuration.

Draw this on the whiteboard

Open the OChem Board whiteboard — benzene rings, wedge/dash bonds, and a clickable periodic table built in. No account needed.

Open the whiteboard →