My money is that
1) /opt/msp430/bin is not in $PATH
verify: echo $PATH
2) you do not have the execute permission
verify: ls -l `which msp430-gcc`
3) (this is cygwin and a VC dll) dependency is missing
verify: strace `which msp430-gcc`
(If you are on cygwin, make sure to check #3).
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