- You can write the two-step mechanism for the SN1 mechanism using the curved electron-pushing arrow formalism, and distinguish it from that for the one-step SN2 mechanism.
- You
understand how to identify likely substrates for an SN1
reaction: tertiary carbon or another structural feature that adds
electron density to the carbocation; presence of a very good
leaving group (not alkoxide or hydroxide, but protonated alcohol
or water as LG is OK); use of a polar solvent to promote
ionization.
Visualization: Carbocation Stabilization and SN1 Reactivity
- You
understand that formation of the carbocation can lead to
stereochemical mixtures in the product when the nucleophile can attack
different sides of the carbocation. You can correctly specify the
stereochemical outcome for any SN1 reaction.
Visualization: Stereochemistry in substitutions
- You
recognize the capacity for alkyl and hydride shifts (leading to more
stable carbocations) in SN1 reactions.
- You know
that in every substitution reaction, a competing elimination is going
to occur.
Visualization: LUMO of tBuCl
- You
understand factors that may promote elimination: steric
inaccessibility of carbon; base (vs. nucleophile) strength; solvent
polarity, overlap of C-H electrons with either empty p orbital (E1) or
with the backside of the C-LG bond (E2).
- You know
that eliminations usually follow the Zaitsev rule to give the
more-substituted alkene.
- You understand the mechanistic requirement that E2
eliminations must adopt an anti-periplanar arrangement of H and halide
for elimination, and the stereochemical consequences of this.
- You can apply the anti-periplanar requirement to
eliminations from cyclohexane rings, including the impact of sterically
demanding substituents on reactivity.
Recommended
end-of-chapter problems: 7-25, 7-28, 7-30, 7-32, 7-35, 7-40, 7-42, 7-46, 7-53, 7-57, 7-60
.
Worked Problems:
Worked Problem 1
Worked Problem 2
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