Enantioselective intramolecular amidation of aliphatic sulfonamides was achieved for the first time by means of chiral carboxylatodirhodium(II) catalysts in conjunction with PhI(OAc)₂ and MgO in high yields and with enantioselectivities of up to 66% (Scheme 3, Table 1). The best results were obtained with [Rh₂{(S)‐nttl)₄] and [Rh₂{(R)‐ntv)₄] as catalysts ((S)‐nttl=(αS)‐α‐(tert‐butyl)‐1,3‐dioxo‐2H‐benz[de]isoquinoline‐2‐acetato, (R)‐nto=(αR)‐α‐isopropyl‐1,3‐dioxo‐2H‐benz[de] isoquinoline‐2‐acetato). In addition, these carboxylatodirhodium(II) catalysts were also efficient in intramolecular amidations of aliphatic sulfamates esters, although the enantioselectivity of these latter reactions was significantly lower (Scheme 4, Table 3).