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Whole, undamaged garlic cloves actually have very little smell. The intense aroma and sharp flavor are only created when the plant's cells are physically ruptured.
Inside intact garlic cells, an enzyme called alliinase is stored separately from an amino acid derivative called alliin. When you chop, crush, or chew the garlic, these cells break, allowing the enzyme and compound to mix. This chemical reaction rapidly generates allicin, the volatile sulfur compound responsible for garlic's pungent bite.
Allowing chopped garlic to rest for 10 minutes before heating gives the alliinase enzyme maximum time to produce allicin before heat deactivates it.
© American Chemical Society