Learn · Organic Chemistry

SN1 vs SN2: how to tell the difference

The four factors that decide whether a substitution goes by SN1 or SN2: substrate, nucleophile, solvent, and leaving group.

Quick answer SN2 is one concerted backside step — 1° substrate, strong nucleophile, aprotic solvent, inversion. SN1 is two steps through a flat carbocation — 3° substrate, weak nucleophile, protic solvent, racemization.

Both convert R–LG into R–Nu; four clues on the substrate and conditions decide the pathway and the stereochemistry.

Methyl / 1° → SN2
3° → SN1
Strong Nu → SN2
Weak Nu → SN1

Open carbon + strong Nu → SN2; stable cation + weak Nu → SN1.

1. SN2 Happens in One Concerted, Backside Attack

Bimolecular (rate = k[substrate][nucleophile]): the nucleophile attacks 180° opposite the leaving group in a single step, inverting the carbon.

Bromomethane — hydroxide approaches from the face opposite Br.
One concerted step: HO⁻ bonds as C–Br breaks (no intermediate).
Methanol — the carbon has inverted through the transition state.

2. A Crowded Carbon Shuts Down the SN2

Each alkyl group added to the reacting carbon blocks the backside approach, so the rate collapses from methyl down to tertiary.

Methyl — fastest SN2
1° (ethyl) — fast
2° (isopropyl) — sluggish
3° (tert-butyl) — no SN2

SN2 rate: methyl > 1° > 2° » 3° — the exact opposite of SN1.

3. SN1 Ionizes First, Through a Flat Carbocation

Unimolecular (rate = k[substrate]): the leaving group departs first to a flat sp² carbocation, favored by the 3°/resonance substrates SN2 can't touch.

tert-Butyl bromide — a tertiary substrate.
Slow step: Br⁻ leaves → flat 3° carbocation (rate-determining).
Fast step: water adds, then deprotonates → tert-butanol.

4. SN1 Racemizes While SN2 Inverts

SN2's one-sided attack inverts a single enantiomer; SN1's flat cation is hit on both faces, scrambling it to a racemic mixture.

(R)-2-bromobutane (single enantiomer)
SN2 → inverted alcohol only
SN1 → this and its mirror image (racemic)

5. Nucleophile, Solvent, and Leaving Group Break the Tie

For borderline 2° carbons: strong anionic Nu + polar aprotic solvent push SN2; weak neutral Nu + polar protic solvent push SN1; both need a good leaving group (I⁻, OTs).

Cyanide — strong Nu (SN2)
Ethoxide — strong Nu (SN2)
Water — weak Nu (SN1)
Iodide — excellent leaving group

6. Summary

SN2: one step · backside · inversion · methyl/1° · strong Nu · aprotic. SN1: two steps · flat carbocation · racemic · 3° · weak Nu · protic. Read the substrate first.

A textbook SN2: primary ethyl bromide + a strong nucleophile (cyanide) in acetone → propanenitrile, with inversion.

Worked example

Problem. Does 1-bromopropane + NaCN react by SN1 or SN2, and what is the product?
  1. The substrate is 1° — a 1° carbocation is far too unstable for SN1.
  2. Cyanide is a strong, unhindered nucleophile → clean backside SN2.

Answer. Butanenitrile, by SN2 (rate depends on both the substrate and CN).

Quiz yourself

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SN1. Its rate law is rate = k[substrate], with no nucleophile term, because the slow step is the substrate ionizing to a carbocation before the nucleophile ever gets involved. In SN2 the nucleophile is in the rate-determining transition state, so doubling it would double the rate.

It went by SN1. The flat, sp² carbocation intermediate can be attacked from either face at nearly equal rates, scrambling the stereocenter into a ≈50:50 mixture. A pure SN2 would have inverted the center to give a single enantiomer instead.

Same feature, opposite consequences: three methyl groups crowd the reacting carbon. That steric bulk blocks the backside approach an SN2 needs (no room for the nucleophile), but it also stabilizes the resulting tertiary carbocation, which is exactly what the SN1 rate-determining step requires.

A polar aprotic solvent such as DMSO, DMF, or acetone. It dissolves the ionic reagents but can't hydrogen-bond to the anionic nucleophile, leaving it "naked" and highly reactive for backside attack. A polar protic solvent would instead solvate the nucleophile (slowing SN2) and stabilize a carbocation (favoring SN1).

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