Exceptions, Paradoxes, and Their Resolutions in Chemical Reactivity.

Progress in chemistry has primarily been framed through inductive processes, leading to the frequent emergence of exceptions and unexpected reactivities. These anomalies─ranging from surprising reactivity trends and paradoxical understandings to unanticipated parameter influences and unexpected successes or failures in synthetic methods─offer valuable insights that can drive scientific discovery. While it is commonly accepted that such exceptions can drive progress, many have been passively accepted without being explored for opportunities. Although numerous chemists have addressed exceptions and refined chemical models and theories, employing a systematic framework for actively exploring and understanding the underlying causes of exceptions could resolve paradoxes in broader contexts and create a greater impact than treating anomalies as isolated occurrences. This perspective demonstrates a proactive epistemic approach to uncovering the opportunities presented by exceptions and promotes deliberate, thoughtful engagement with paradoxes and anomalies. While the examples primarily focus on physical organic chemistry, the concepts are broadly applicable across various fields in chemical science. The thinking framework presented here is neither exhaustive nor prescriptive, but it outlines one of many potentially possible ways to inspire further development in how these anomalies could be harnessed for advancement.