Actully we have a easiest way,suppose you have dataset
like
dataset=Dataset[{{"a", 10}, {"b", 11}, {"c", 12}, {"d", 5}, {"e", 99}}]

You can add a column name
dataset[All, <|"char" -> 1, "freq" -> 2|>]

Performance
But if you have a large data set,I have compared FIVE solution here
dataset = Dataset[RandomInteger[100, {200000, 2}]];
AbsoluteTiming[dataset[All, <|"col1" -> 1, "col2" -> 2|>];]
AbsoluteTiming[dataset[Map[AssociationThread[{"col1", "col2"} -> #] &]];]
AbsoluteTiming[dataset[All, Apply[<|"col1" -> #, "col2" -> #2|> &]];]
AbsoluteTiming[dataset[All, Association[Thread[{"col1", "col2"} -> #]] &];]
AbsoluteTiming[dataset[All, AssociationThread[{"col1", "col2"} -> {1, 2}]];]
{2.83872, Null}
{0.968482,Null}
{2.15222, Null}
{1.73927, Null}
{3.03586, Null}