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In a small bowl, combine buttermilk and gelatin; set aside to soften. In a small saucepan over low heat, combine cream, 1⁄4 cup sugar, 2 tablespoons liqueur, and vanilla bean. Bring to a simmer. Remove from heat. Stir in buttermilk mixture, whisking until gelatin solids are dissolved; strain, discarding solids. Evenly divide mixture among 6 (13⁄4-ounce) silicone molds. Refrigerate for 4 hours. To unmold, gently pull edges of molds with fingers to loosen. Invert to serve. In a small saucepan, combine peach, remaining 2 tablespoons sugar, and remaining 2 tablespoons peach liqueur. Bring to a boil over medium-high heat. Boil 3 minutes or until sugar dissolves. Let cool completely. Serve peach sauce over panna cotta.