Spray a lg skillet w/ cooking spray, place over med-high heat. Brown chops on both sides, pour off any fat.
In bowl, combine brown sugar, cinnamon, cloves, tomato sauce , reserved peach syrup, and vinegar, mix well.
Sprinkle chops w/ salt and pepper and place in a 4-quart slow-cooker. Place peaches on top of chops. Pour sauce over peaches. Cover and cook on low for 4-6 hrs, or until chops are cooked through, but tender.