if(sum in naturalNumbers)
obviously isn't valid syntax. You're using something like 'for in' and with an int instead of an object.
What you want is:
if ([naturalNumbers containsObject:@(sum)]) {
Which asks the array if it contains an NSNumber
instance containing the sum
.
Your method doesn't name the second parameter, which is legal but not encouraged. It would be better as:
-(NSString *)resultsOfRoll:(int)firstRoll secondRoll:(int)secondRoll