No, the 1/3, 2/3 only applies to your Property Tax/Mortgage Interest (and only because your property is titled that way).
You can divide your Medical Expenses any way that you agree on (since they were paid from a joint account).
However, if your spouse paid 5K into an HSA, she would want to report at least 5K in Medical Expenses, for example.
If her insurance premiums were 'pre-tax' they would not be deductible anyway.
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