Ok, I would round to 2 signficant figures in your first example because 1.223 and 16 are your two rounded figures, but 16 only has two significant digits, and you use the number with the smallest amount of significant digits. 1 mol is not rounded because it is an exact quantity. 1 mol = 1.0 mol = 1.0000000000000 mol, etc. In the ratio 1 mole/16 grams O2 (which now reading it is actually wrong, there are 32 g/mol O2), you are relating MW to that precise quantity, but 32g O2 aren't what's actually in a mole of O2; it's more like 31.998.. etc
For your second example, the difference between the first and second statement is the period after the 1 in the second question. In the first question, you interpret the 1 mile like you interpreted the 1 mol in the last question. However, in the second question, the decimal following the 1 confers an implied estimation on the amount of miles you have, so you have 1 significant digit, and your answer would be 2 km.