Windows doesn’t have inbuilt tools or commands to get MD5 sum. But Microsoft provides a tool that you can use on windows to get MD5 sum for any file.
You can download File Checksum Integrity Verifier (FCIV) utility from here.
Download and extract this utility to C:\Tools and use following commands to get the MD5 sum:
C:\Tools>fciv.exe –add sample.zip -md5
// File Checksum Integrity Verifier version 2.05.