UK Immigration Law
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The UKBA will reject an application from an applicant from a country other than their home country if they do not have leave to remain in that country. So, if your husband has sufficient leave to remain in the US to enable him to apply for a spouses visa (ie. Settlement) and that leave to remain shall not expire during the course of the application then he would be able to apply.
If as you have stated his visa is expiring now then I would not advise applying from the US because he would not have leave to remain at the time of application, which would mean that they would reject the application. It would be complicated further if he left the US after the expiring of his visa as this suggests a chequered regard for immigration rules which the UKBA would not look to kindly on and would probably result in putting them on an adversarial footing.
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