Insurance is all about sharing risk. I'm unwilling to risk my house burning down. I know it's not likely that it will, but if it does, the loss would be devastating to me. Most people feel that same way, so we all get together and share the risk. In return for a promise that none of us will ever have to suffer the catastrophic loss, we all chip in a small fraction of our home value every year and create a pool from which to compensate those who are unlucky enough to have their house burn down. What the insurance companies do is essentially act as a market maker for these risk pools. Rather then me have to go out and find 1,000,000 people to share the risk with, the insurance company does it for me (and takes a small fraction of the pool as their profit)
Now, the insurance company doesn't want risk any more than I do. To avoid that, they need to make sure they charge enough in premiums to pay off all likely claims. And to do that, they need to be able to accurately evaluate the probability of a claim. For open-ended liabilities (i.e. a replacement cost homeowners policy), they also need to be able to accurately estimate the maximum size of a claim.
For things like fire insurance on houses, there's tons of history to base these estimates on. They've insured hundreds of millions of houses, and have been doing it for many years. They've paid off millions of claims. For a given location, type of construction, age of house, etc, they know exactly what the risks are and can price the policy accordingly. Ditto for group health insurance, automobile insurance, and so on.
But, bitcoins? Insurance companies have no clue about bitcoins. There's essentially zero history establishing what they're worth, and likewise there's essentially zero history establishing what the risks are. How often do bitcoins get stolen, lost, destroyed, etc? What best practices exist to reduce the risk of these losses? What types of fraud might exist in bitcoin loss claims, and how can the company determine if a claim is fraudulent or not? For the most part, there are no answers to these questions. At least not today. Thus, it's unlikely that you would be willing to find an insurance company willing to accept any bitcoin risk. And if you did, it would probably come with a very high premium, fixed liability limit, and onerous conditions. For a large insured value, you might also find that the only way a company would take the risk would be if there was a consortium of companies which all took a part of the risk (this is what places like LLoyds of London are all about).