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Kaido did use it his sky splitter moment with Mama.

Dragon and Garp are pretty much guaranteed to have it IMO due to the "He inherited it" moment by Garp towards Luffy. The chances of at least one of these 2 having it is basically 100%. So we have Roger D. Portgas D. Dragon D./Garp D. Luffy D. I'm gonna go on a limb and speculate Law is highly...

Those techniques deal damage internally. Rokuogan seems like the primitive version of haki beams that bypass defense, just like Tekai is a primitive version of regular defense CoA haki.

He used haki. The only way to hurt the rubber man is through haki attacks, cutting, attacks that affect the body internally etc. The club is spiked but I don't think the spikes punched through Luffy, so it's likely he used haki and the sparks seems to support that.