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Cook sugar in a medium saucepan over medium-low heat, undisturbed, until mostly melted, 6–8 minutes. Stir edges into the center with a heatproof spatula; cook, swirling pan occasionally, until caramel turns dark amber, about 2 minutes. Stir in rhubarb and 3 Tbsp. vinegar. Partially cover and cook, stirring occasionally, until rhubarb is very soft, 8–10 minutes. Transfer to a small bowl; let cool. Stir in remaining 1 tsp. vinegar; season with salt and pepper.