Typical reaction steps used in chemical synthesis (that is, not detonations) are extremely improbable and rare.
That is, a molecule (or ion, radical...) can collide with a step candidate every nanosecond (gas) or picosecond (liquid), but the reaction takes an hour to complete. Consistently, the reaction step can need to cross an activation energy of 30kJ/mol for instance, but the temperature is only RT=3kJ, so the necessary heat is obtained in one attempt over exp(10) to make it simple. Even more difficult: the activation energy corresponds to the best possible combination or positions and orientations and conformations of both molecules.
So the species don't "know" nor "sense" what would be their best match. They just collide randomly; the encounters are rarely fertile when they happen to proceed at the most favourable carbon position, orientations and so on; and when the conditions are less favourable, say at a worse carbon, the encounters are even more sterile.