Named reactions index

Aldol addition

specified-next: primitive mechanism is explicit; guarded v2 executable rule set is not yet promoted.

Interactive Route Player

Use next/prev to step through the route: first the current state is shown without highlight, then the next ownership move is previewed, then the move is executed. If a route snapshot changes several ownership records, the player unfolds them one at a time. Drag a node to fix it; double-click a fixed node to release it.

HEG v2 State Sketches

These panels are rendered from ownership-structured HEG v2 objects. For specified-next examples they are state sketches, not yet products of executable v2 rules.

Aldol substrate HEG sketch

Aldol substrate HEG sketch

Carbanion/enolate-like donor plus aldehyde carbonyl acceptor.

Aldol route step 1

Aldol route step 1

Primitive snapshot: donor lone-pair resource has become the new C-C shared pair.

Aldol route step 2

Aldol route step 2

Carbonyl pi resource has moved to oxygen, giving the alkoxide state.

Aldol route protonated product

Aldol route protonated product

Alkoxide lone pair has become an O-H shared pair in the protonated beta-hydroxy product sketch.

DPO-like Step Panels

Each primitive snapshot is shown as L/K/R. Red marks the ownership edge removed from L, orange marks the halfedge whose owner changes, and green marks the ownership edge created in R. K keeps the common atoms, halfedges, pair objects, and unchanged ownership records. For specified-next examples this is an explanatory span derived from route snapshots, not yet a checked executable rule application.

Aldol addition route step 1

Aldol substrate HEG sketch -> Aldol route step 1

h8: a1 -> a5

L

L panel

K

K panel

R

R panel

Aldol addition route step 2

Aldol route step 1 -> Aldol route step 2

h9: a5 -> a6

L

L panel

K

K panel

R

R panel

Aldol addition route step 3

Aldol route step 2 -> Aldol route protonated product

h16: a6 -> a8

L

L panel

K

K panel

R

R panel

Reaction Sketch

reaction sketch

Specified as primitive HEG ownership moves; an older EFG/native-HEG formose aldol rule exists, but this v2 guarded primitive version is a next implementation target.

Mechanism Flow

mechanism flow

Primitive Steps

enolate carbon lone pair forms C-C sigma pair

lone pair to shared pair: LP(C_alpha) -> sigma(C_alpha,C_carbonyl)

requires enolate/carbanion resource and no existing C_alpha-C_carbonyl shared pair

acceptor carbonyl pi pair becomes alkoxide lone pair

shared pair to lone pair: pi(C_carbonyl,O) -> LP(O)

requires acceptor C=O carbonyl resource

alkoxide lone pair becomes O-H sigma pair

lone pair to shared pair: LP(O) -> sigma(O,H)

requires proton donor and no existing O-H shared pair

Guards and Alternatives

Guards

  • alpha donor must be an enolate/carbanion resource, not any carbon lone pair.
  • acceptor must contain a real carbonyl pi resource.
  • C-C bond must be absent before attack.
  • product admissibility should be checked after each grouped rule.

Route probes

  • Self-aldol vs crossed-aldol routes are chemically meaningful alternatives once donor and acceptor carbonyls are distinguishable.
  • Unsymmetrical ketones add alpha-position regioselectivity; this requires role guards beyond atom labels.

Files