The new, axially chiral borates 2, 9, and 11 and boronates 3–6 and 12 are synthesized in good yields. They are representatives of three different structural types. The bicyclic borates 2 and 9 are homochiral propeller compounds; their exclusive formation is used to increase the enantiomerical purity of 1. Especially the borates are efficient Lewis acidic catalysts for stereoselective Diels–Alder reactions. The new seven-membered boron compounds 4, 5, 6, and 12 are interesting reagents for different asymmetric synthetic steps. Activated vinylboronates 31 can serve as efficient cyclophiles in [3+2] cycloaddition reactions with methylenecyclopropane 27 giving borylated methylenecyclopentanes 32.