A tricoordinate borenium ion has received considerable attention in recent years for its applications in Lewis acid catalysis. Over the years, asymmetric catalysis mediated by a chiral borenium ion has also been developed. To stabilize the electron-deficient boron atom, a series of chloroborane masked borenium ions featuring the symmetrical [B-Cl-B]+ linkage are prepared and utilized as the catalyst for the enantioselective Diels-Alder cycloaddition of cyclopentadiene and 2,2,2-trifluoroethyl acrylate. The presence of a Cp* ligand is critical in realizing the cyclic diboron compounds, and the stability of the resulting [B-Cl-B]+ cation is dependent on the steric bulkiness of the oxazolidinone moiety. The stereoselectivity of the Diels-Alder cycloaddition is controlled by the substituents of the chiral oxazolidinone ligand and could be further improved via the coordination of SnCl4 at the bridging chloride of the [B-Cl-B]+ cation.