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Photosynthesis is certainly critical, because neither plants nor animals could exist on Earth without it (ultimately, all animal derive their food from plants), but photosynthesis is a network of numerous reactions - which ONE is most important? Same applies to all of the metabolic processes that allow human beings and other animals to function -- ATP or Acetyl coA perhaps?

I'll go with the largest and most important SYNTHETIC chemical reaction, which I believe is unquestionably the Haber-Bosch reaction for making ammonia, a critical synthetic fertilizer without which the Earth could not support more than a modest fraction of the people living on it today:

N2 + 3H2 --> 2NH3

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