The purpose of the {enumerate}
environment is to number things algorithmically. If you really want the numbers to appear as shown in your question, I can't identify what algorithm you want to be used. For the example you show, I think the easiest method is just to program the labels yourself instead of trying to program LaTeX to do it. I would just do it this way:
\begin{itemize}
\item[1.] Item
\begin{itemize}
\item[2. ] Item
\item[3a. ] Item
\item[3b. ] Item
\item[4. ] Item
\end{itemize}
\item [5. ] Item
\end{itemize}
With LaTeX, the quickest path to a solution often involves brute force :-)