You first see Rukia use her Shikai in episode 117.
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Naruto learns to use Wind Release: Rasenshuriken in Naruto Shippuden episode 88. The episode is called "Wind Release: Rasenshuriken!"
14th Episode of Naruto Shippuden.. While Fighting With Kisame...
in naruto shippuden 184
he learns it in episode 21, but doesn't use it until 22.