You can iterate through the dictionary and unpack the key and the value at the same time this way:
b = {}
for key, value in a.items():
if value in key:
b[value] = key
This will generate your wanted solution. It does that by unpacking both the key and the value and checking if they match afterward.
You can also shorten that code by using a dictionary comprehension:
b = {key:value for key, value in a.items() if key in value}
This short line does the exact same thing as the code before. It even uses the same functionalities with only one addition - a dictionary comprehension. That allows you to put all that code in one simple line and declare the dictionary on the go.