It's been quite a fact that some of the commands cannot be accessed, due to users Matlab version or it may be due to necessary toolboxes associated with that? How exactly we can find the use of particular command for particular version or toolbox?. For e.g If an user wants to use syms command, from which Matlab version the command is used?
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There is no mechanism for this, other than carefully going through the documentation for each release.
The particular example you give, syms(), is part of the Symbolic Toolbox, which is an optional (extra-cost) toolbox in any Academic or Commercial license, but which is included in each Student Version (but not installed by default.) syms() predates the switch to MuPAD in R2009b (I think it was), back to when Maple was the symbolic engine. syms() dates back to at least R13SP2.