The Decomposition of Aromatic Sulfinyl Sulfones (Sulfinic Anhydrides). The Facile Homolysis of a Sulfur-Sulfur Bond

Disulfides as Sulfonylating Precursors for the Synthesis of Sulfone‐Containing Oxindoles

“…of persulfate oxidant [Scheme , Eq (5)]. It was deduced that compound 4 was further oxidized to sulfinyl sulfone ( 8 ), which could undergo spontaneous homolytic S−S bond cleavage to yield a sulfonyl radical ( A ) and a sulfinyl radical ( 9 ) . On the other hand, sulfinyl radical intermediate 9 is also generated from the homolytic cleavage of the S−S bond in disulfoxide 7 ,.…”

Synthetic exploration of sulfinyl radicals using sulfinyl sulfones

“…However, their structure and reactivity have only been sporadically investigated 27 – 30 ; the perception that sulfinyl sulfones are unstable, hard-to-handle materials, along with a lack of reliable methods for their synthesis, has deterred research and restricted their occasional use as electrophilic sulfur sources 31 – 33 . A single report suggested that their thermal decomposition might proceed via homolytic fission, generating two distinct sulfur-centered radicals—a sulfinyl radical and a sulfonyl radical 34 . As sulfonyl radicals are known to undergo facile addition to π -bonds 17 – 19 , sulfinyl sulfones appeared to be well suited for our envisioned strategy.…”

Multicomponent Assembly of α,α‐Bis‐Sulfonyl Arylketones and Multiple Substituted Conjugated Dienes Induced by Visible‐Light Irradiation without Additives and Photocatalysts

“…Schemes 5e and 5 f confirmed that 3 aa was formed via the intermediate acetylenic sulfone product 6 aa. Considering the conversion of sulfinic acids to sulfinyl sulfone [14] in conjunction with the results of Schemes 5g and 5 h showed that this photo-promoted tandem process was initiated by sulfonyl radicals derived from sulfinyl sulfones in the presence of visible-light irradiation. On the other hand, the possibility that the generation of product 3 aa underwent the cationic process through 6 aa and 2 a was also ruled out by other designed control experiments (see the ESI for details).…”

“…On the other hand, the possibility that the generation of product 3 aa underwent the cationic process through 6 aa and 2 a was also ruled out by other designed control experiments (see the ESI for details). Performing similar control experiments (Schemes 5i-5 l) to investigate another multimolecular reaction mechanism produced the following results: (1) the substituted conjugated diene product 5 aa cannot be formed without visible-light irradiation (Scheme 5i); (2) assembly of multiple substituted conjugated dienes may require the presence of sulfinyl sulfone, acetylenic sulfone, and bis(arylsulfonyl) ethylene intermediate products (Scheme 5j and 5k); [14] and (3) the O-atom of the sulfonate group in the product 5 aa derives from H 2 O (Scheme 5l).…”