The idea is that when when frozen, or even chilled, the starch crystalises (and some papers indicate glucose can promote this), in the same way as cooked potatoes, pasta and rice are similarly affected. The process is irreversible, hance the foods can be warmed up.
Starch in bread is broken down by amylase in saliva and maltase in the small intestine to glucose.
Resistant starch though cannot be hydrolysed by these enzymes, and so is broken down in the large intestine. However, this time, its fermented by bacteria to acetyl CoA.
A bit of O-Level biology as a reminder
Some have looked at this phenomenom from the perspective of reducing colorectal cancer.
All three procedures investigated, freezing and defrosting, toasting from fresh, and toasting following freezing and defrosting, favourably altered the glucose response of the breads. This is the first study known to the authors to show reductions in glycaemic response as a result of changes in...
pubmed.ncbi.nlm.nih.gov
Freezing bread could reduce the glycaemic response by almost 31%. All the media reports, TikToks etc are based on this 2008 paper. The paper reports an effect, in a small group. The supposition is that the change is due to the development of RS4. But likely, most of the starch just stays as starch. The study was made using homemade bread, so the effect might be different with commercial batches.
There are more studies looking at potatoes and rice. In potatoes, the RS4 content is increased by 50% when a cooked potato is chilled. What that means is a shift in resistant starch content from about 3% of the potato to 6%.
I don't think the change is all that significant for how you eat food now. Its more significant in the context of increasing the RS content in uncooked foodstuffs.