Exceptions, Paradoxes, and Their Resolutions in Chemical Reactivities

Chemists have long utilized theories and models to rationalize empirical data and predict outcomes in new chemical systems. Unexpected reactivities often present themselves as exceptions or paradoxes, highlighting gaps in our current understanding and the limitations of (then) existing models. Rather than something to be disregarded, these exceptions offer valuable insights that can lead to the refinement of theories and the resolution of paradoxes, ultimately fostering scientific discovery. While the concept of scientific discovery described is not new, practically, it remains significantly underappreciated in the field of organic chemistry. This perspective article postulates possible epistemic origins of such unexpected chemical reactivities across various contexts, proposing a systematic approach to addressing these anomalies. Through a compilation of origins, supported by specific modern examples, this work aims to lay the groundwork for more comprehensive thinking that will help the field navigate future exploration. While the illustrative examples presented herein focus on physical organic chemistry, the concepts discussed are universally applicable across different fields in chemical science.