Another noteworthy advancement in the domain of assembling sultam heterocyclic fragments involves an intramolecular homolytic substitution reaction (SNi) near the sulfur atom. This method has been successfully employed to synthesize benzannelated γ-sultam 131 with a substituent at the C(3) position, achieving high enantiomeric purity. The synthetic transformation entails the addition of TMSCN to the double C=N bond of sulfinyl imine 132, utilizing ytterbium triflate as a catalyst. However, the resulting nitrile 133 was unsuitable for intramolecular homolytic substitution due to the preferential addition of o-aryl debrominated radical to the nitrile group rather than the sulfinamide group (Scheme 18). Consequently, to overcome this limitation, the nitrile group of compound 133 was converted into the N-Boc-protected aminomethyl-containing derivative 134, which facilitates the subsequent formation of cyclic sulfinamide 135 with 78% yield and high diastereomeric excess (de) under the influence of AIBN and n-Bu3SnH in toluene. Furthermore, the resulting sulfinamide 135 could be efficiently oxidized with mCPBA to produce sultam 131 in 99% yield. The reaction sequence relied on the preparation of mesylates 137a-e (89-95% yield) from hydroxy nitriles 138 via mesylation in the presence of Et3N in CH2Cl2. Subsequently, sulfur atom incorporation was achieved via nucleophilic substitution of 137 with t-BuSH in the presence of a base (Scheme 20). Most tert-butyl sulfides 139 were obtained with good yields, while better results were obtained in the case of using KSAc for cyclohexane derivative 139d for the preparation of 140d. Oxidative chlorination of tertbutyl sulfides 139a-c,e and thioacetate 140d was efficiently achieved using molecular chlorine (Cl2) in a CH2Cl2-H2O mixture (2:1, v/v), resulting in the formation of the corresponding β-cyanosulfonyl chlorides 141a-e in 61-82% yield (Scheme 20).