Preheat your oven to 375°F (190°C). Pat the chicken thighs completely dry with paper towels and season them generously on all sides with salt and pepper.
In a medium bowl, whisk together the reserved juice from the can of pineapple, soy sauce, brown sugar, chicken broth, rice vinegar, grated ginger, minced garlic, and sesame oil to create the sauce. Set aside.
In a large, oven-safe skillet or Dutch oven, heat the olive oil over medium-high heat. Carefully place the chicken thighs skin-side down. Sear, undisturbed, for 5-7 minutes, until the skin is golden brown and crispy. Flip the chicken and sear for another 2-3 minutes. Remove the chicken from the skillet and set it aside on a plate.
Pour out all but one tablespoon of the rendered fat from the skillet. Add the uncooked rice to the skillet and toast it for about a minute, stirring constantly, until it becomes fragrant and slightly translucent.
Pour the prepared sauce mixture over the rice and stir, scraping up any browned bits from the bottom of the pan. Scatter the pineapple chunks evenly over the rice.
Nestle the seared chicken thighs on top of the rice and pineapple mixture, skin-side up. Pour any accumulated juices from the chicken plate back into the skillet.
Bring the liquid to a gentle simmer on the stovetop. Once bubbling, cover the skillet tightly with a lid or heavy-duty aluminum foil and transfer to the preheated oven. Bake for 30 minutes.
After 30 minutes, remove the cover and bake for another 15-20 minutes, or until the rice has absorbed all the liquid and the chicken is cooked through and beautifully glazed.
Remove the skillet from the oven and let it rest, uncovered, for 10 minutes. This allows the rice to finish steaming and the chicken juices to redistribute.
After resting, fluff the rice gently with a fork. Garnish generously with sliced scallions and toasted sesame seeds before serving.