You've mentioned in the comments that you have duplicate entries. We can work with this. Take your favorite method of generating the list of tuples, and expand it into a for loop:
from itertools import izip
dictionary = {}
for k, v in izip(List[::2], List[1::2]):
if k not in dictionary:
dictionary[k] = set()
dictionary[k].add(v)
Or we could use collections.defaultdict so we don't have to check if a key is already initialized:
from itertools import izip
from collections import defaultdict
dictionary = defaultdict(set)
for k, v in izip(List[::2], List[1::2]):
dictionary[k].add(v)
We'll end with a dictionary where all the keys are sets, and the sets contain the values. This still may not be appropriate, because sets, like dictionaries, cannot hold duplicates, so if you need a single key to hold two of the same value, you'll need to change it to a tuple or a list. But this should get you started.