Can and should are two very different things. The two have different absorption rates for different things. You may overdose or it may be totally ineffective. There may be toxic contaminants that taken orally might not be absorbed much, so its relatively safe, but taken rectally might be absorbed into the blood stream. There's also the sanitation issue. The mouth is generally better at capturing and keeping infections out of the body than the rectum, so you may need to sanitize the pills which might be difficult if you don't want them to dissolve. And relatedly, there's the matter of the inactive ingredients. They're designed to be swallowed, but may cause issues left behind in the rectum. Most pills that are swallowed just use starches which isn't a big deal, but to make things dissolve quickly there are other ingredients including sometimes sugars which could encourage microorganism growth if you don't sanitize them or some ingredients may trigger diarrhea or other reactions.
There's usually not research done on a drug taken sublingually as to how it would affect a person rectally, so it's usually not going to be well known.
That said, ask your doctor. If there is any data about doing it, they would be more likely to know.