You could try:
>>> d = OrderedDict([('a', 1), ('c', 3), ('b', 2)])
>>> d
OrderedDict([('a', 1), ('c', 3), ('b', 2)])
>>> d2 = OrderedDict([('__C__', v) if k == 'c' else (k, v) for k, v in d.items()])
>>> d2
OrderedDict([('a', 1), ('__C__', 3), ('b', 2)])
与恶龙缠斗过久,自身亦成为恶龙;凝视深渊过久,深渊将回以凝视…