The author of this article is somewhat wrong - in .NET 4.5 the AsynchronousProcessing property is ignored because it is no longer required. You can just start calling the Async methods of SqlClient without any special connection strings.
Whether the operations will execute asynchronously, depends on the database provider. For example, the default implementation of DbCommand.ExecuteDbDataReaderAsync actually executes synchronously and blocks the calling thread. SqlCommand overrides this method and executes asynchronously.
Unfortunately, NpgsqlCommand doesn't override this method so you are left with synchronous execution only.