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Sister could file for divorce before signing and obtain a quick court order requiring the company to issue the buyout check in joint name. Then the proceeds can be set up in a trust fund that will protect both of them, and then they can dismiss the divorce and stay together. Or something like that.
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If husband is unwilling to voluntarily assign her an interest, or create a trust, the divorce is just a tactic to accomplish what you mention. It will require a lawyer, and there is no guarantee that it can be done. It's a tough legal situation.