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I am unable to understand which one is the correct?

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The choice between who[ever]/whom[ever] comes down to the role of the relative pronoun in the subordinate clause. In this case, it will be nominative rather than oblique since who is linked to he by was.

Now, for whoever vs who, whoever implies an indefiniteness which isn't here so the correct phrase would be “When he first entered the classroom no one knew who he was.”

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