Betulin and betulinic acid are lupane-type secondary metabolites found in birch bark. These triterpenoids and their derivatives are known for their remarkable antitumor, antidiabetic, anti-inflammatory and antiviral properties. Among many possible functionalization possibilities, the C–H activation is underdeveloped in this compound class. Hence, we present here C(16) and C(22) C–H amination followed by functional group transformation that provides heteroatom containing triterpenoid derivatives with better solubility profile. Sulfamate ester 2 was obtained in few steps from betulin (1) and following C-H amination reaction proceeds in the presence of rhodium catalyst, forming oxathiazinane 3, which is versatile precursor for various ring-opening reactions.