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bart · organic chemistry II · day 03 of 07
day 03 · nucleophilic substitution · ≈ 90 minutes

SN1 vs. SN2, decided on sight.

goal — look at any substrate and call the mechanism without guessing.

Yesterday you learned to push arrows. Today you use them. Nucleophilic substitution is two reactions wearing one name, and almost every exam question is really asking which one is running. Get that call right and the product, the rate, and the stereochemistry all fall out for free.

Start with the kinetics, because the rate law is the cleanest tell. SN2 is one concerted step — the nucleophile and the substrate meet in the rate-determining step, so both appear in the rate law:

rateSN2 = k [substrate] [nucleophile]

SN1 goes through a carbocation. The slow step is the substrate losing its leaving group by itself; the nucleophile arrives afterward, off the clock. So only the substrate shows up:

rateSN1 = k [substrate]

That single difference — second order vs. first order — is why your slides call SN2 bimolecular and SN1 unimolecular lecture 06, slide 14. Everything else today is a consequence of it.

the backside attack

In SN2 the nucleophile attacks the carbon directly opposite the leaving group. The three other groups flip through — like an umbrella in the wind — and the product has inverted configuration. This is why it's stereospecific, and why a crowded carbon kills it: there's no room at the back door.

Nu⁻ C :LG⁻ ‡ transition state inversion
SN2 — Nu⁻ enters opposite the leaving group; the substrate inverts.

the four tells

You almost never compute a rate on an exam. You read four features off the structure and let them vote.

factorfavors SN2favors SN1
substrate methyl / 1° — open back side — stable carbocation
nucleophile strong (OH⁻, CN⁻, RO⁻) weak (H₂O, ROH)
solvent polar aprotic (DMSO, acetone) polar protic (water, alcohols)
leaving group good in both — I⁻ > Br⁻ > Cl⁻ > F⁻

The substrate vote is the loudest. substrates are the genuine toss-ups — that's when the nucleophile and solvent break the tie your notes · pg. 7.

SN2 = 2 things

Two molecules in the slow step. Two-faced result.

Bimolecular rate law, backside attack, inverted product — all "two." SN1 stands alone: one molecule, one carbocation, a racemic mix.

quick checks — answer, then reveal

Q1 Which is most likely to react by SN1: 2-bromobutane, tert-butyl bromide, or bromomethane? answer
tert-Butyl bromide. It's a 3° substrate, so losing Br⁻ gives a stabilized 3° carbocation — the SN1 slow step. Bromomethane is the SN2 extreme (wide-open back side); 2-bromobutane is the 2° toss-up that depends on conditions.
Q2 You run a 2° substrate with NaCN in DMSO. Which mechanism wins, and what happens to the stereocenter? answer
SN2. CN⁻ is a strong nucleophile and DMSO is polar aprotic — both push SN2, overruling the ambiguous 2° substrate. The stereocenter inverts via backside attack.
Q3 Why does an SN1 reaction on a single enantiomer give a racemic mixture? answer
The carbocation is flat. The sp² intermediate is planar, so the nucleophile attacks either face with roughly equal probability — you get both enantiomers, ≈50/50.

end of day 03 — tomorrow: stereochemistry, where today's inversion becomes a tool you reach for.

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