Learn · Organic Chemistry

Deciding by the substrate

Step 1 of the SN1/SN2/E1/E2 decision — let the carbon skeleton rule pathways in or out.

Quick answer Always read the substrate first, because the carbon bearing the leaving group rules whole pathways in or out: methyl and primary carbons go SN2 only, tertiary carbons go SN1/E1/E2 only, and secondary carbons can do any of the four. Allylic and benzylic halides join the SN1/E1 group because their carbocations are resonance-stabilized.
  1. 1. Read the substrate before anything else.

    The carbon bearing the leaving group decides which of the four mechanisms are even possible.

    Methyl → SN2 only
    1° → SN2
    2° → depends
    3° → SN1/E1/E2 only
  2. 2. Methyl and primary carbons go SN2 only.

    They cannot form a carbocation — a methyl or 1° cation is far too unstable — so SN1 and E1 are ruled out.

    1-Bromobutane (1°) — backside attack, SN2
  3. 3. Tertiary carbons go SN1, E1, or E2 only.

    A stable 3° carbocation forms readily, while steric crowding blocks the SN2 backside approach.

    tert-Butyl bromide (3°) — SN2 blocked, cation easy
  4. 4. Secondary carbons are the swing case.

    Any of the four mechanisms is possible, so the nucleophile/base, solvent, and temperature make the call.

    2-Bromobutane (2°) — conditions decide
  5. 5. Allylic and benzylic halides also unlock SN1/E1.

    Their carbocations are resonance-stabilized, so even at a 1°-looking carbon a cation pathway opens.

    Allyl bromide — resonance-stabilized cation
    Benzyl bromide — resonance-stabilized cation

Summary

Substrate first · methyl/1° → SN2 only · 3° → SN1/E1/E2 only · 2° → swing case (conditions decide) · allylic/benzylic → SN1/E1 unlocked by resonance

Quiz yourself

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SN1 needs a carbocation intermediate, and a methyl or 1° cation is far too unstable to form, so only the concerted SN2 pathway is open.

SN2 is ruled out — the crowded 3° carbon blocks backside attack. Only SN1, E1, and E2 remain, favored by the easily formed stable 3° cation.

All four mechanisms are possible at a 2° carbon, so the substrate alone can't decide — the nucleophile/base strength, solvent, and temperature settle it.

Its cation is resonance-stabilized by the adjacent ring (or double bond, for allylic), making the carbocation stable enough for SN1/E1 to occur.

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