Here is your dataframe:
import pandas as pd
df = pd.DataFrame({
'A': ['a.1', 'a.2', 'a.3'],
'B': ['b.1', 'b.2', 'b.3'],
'C': ['c.1', 'c.2', 'c.3']})
Your answer is in the paragraph "Setting with enlargement" in the section on "Indexing and selecting data" in the documentation on Pandas.
It says:
A DataFrame can be enlarged on either axis via .loc.
So what you need to do is simply one of these two:
df.loc[:, 'D'] = df.loc[:, 'B']
df.loc[:, 'D'] = df['B']