🧪

Arrow-Pushing in Organic Mechanisms

Oct 17, 2025

Overview

This lecture covers how to combine the four key arrow-pushing patterns in organic chemistry mechanisms, illustrating correct and incorrect electron movement for reaction mechanisms.

Review of Arrow-Pushing Patterns

  • Four main patterns: proton transfer, loss of a leaving group, carbocation rearrangement, and nucleophilic attack.
  • Multiple arrow patterns can occur in one reaction step.

Example: Combining Patterns in a Reaction

  • Step 1: Proton transfer uses two arrows, indicating proton movement to a reactant.
  • Step 2: Loss of a leaving group is shown by a single arrow with a negative sign over the reaction arrow (e.g., –H₂O).
  • Step 3: Carbocation rearrangement involves shifts (methyl or hydride) to form a more stable carbocation.
  • Step 4: Nucleophilic attack and loss of leaving group can occur simultaneously, depicted by two arrows (one for attack, one for group departure).

Mechanistic Arrow-Pushing: Correct and Incorrect Approaches

  • Arrows should start at electron pairs or bonds and point toward electrophilic centers or leaving groups.
  • Do not start arrows at inappropriate atoms or bonds—incorrect arrows may appear in multiple-choice questions.
  • Electron movement should never violate the octet rule; carbon cannot expand its octet beyond eight electrons.
  • Only adjacent atoms (not distant ones) should be involved in electron shifts.

Key Terms & Definitions

  • Proton transfer — movement of a proton (H⁺) from one species to another.
  • Leaving group — atom or group that departs with a pair of electrons in a reaction.
  • Carbocation rearrangement — shift of a group to stabilize a positive carbon center.
  • Nucleophilic attack — nucleophile donates electrons to an electrophilic atom, forming a bond.
  • Octet rule — atoms (especially carbon) must not have more than eight electrons in their valence shell in organic mechanisms.

Action Items / Next Steps

  • Practice drawing combined arrow-pushing mechanisms for given reactions.
  • Review the four basic arrow-pushing patterns and their correct usage.
  • Prepare for further discussion on mechanism patterns in the next lecture.