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I know that chloroform can be used to make people unconscious, but would that also work with deuterated chloroform, $\ce{CDCl3}$?

My instinct is "yes", but I'm not sure I'm willing to try this experiment on anyone.

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    $\begingroup$ My instinct says the same. $\endgroup$
    – Ivan Neretin
    Commented Sep 18, 2015 at 21:11

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In almost all respects, deuterium behaves like hydrogen, chemically. You can safely drink pure $\ce{D2O}$ in reasonable quantities (though not enough to replace more than ~25% of the $\ce{H2O}$ of the body). In fact, prokaryotes can continue to grow in ~100% deuterated media, albeit more slowly. It does prevent mitosis in eukaryotes in large quantities, though.

Given that similarity, there is no reason to assume any different behavior between deuterated chloroform and that with just protium. But don't knock yourself out trying the experiment, as chloroform is hepatotoxic.

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