Production of Alkyl Aryl Sulfides from Aromatic Disulfides and Alkyl Carboxylates via a Disilathiane–Disulfide Interchange Reaction

Abstract

The results of this study show that disilathiane is an effective mediator in the synthesis of alkyl aryl sulfides with disulfides and alkyl carboxylates. Mechanistic studies suggest that disilathiane promotes cleavage of the sulfur-sulfur bond of disulfides to generate thiosilane as a key intermediate. Diselenides were also applicable to this transformation to produce the corresponding selenides.

Recent Applications of Hexamethyldisilathiane (TMS2S) in Organic Synthesis

“…25 TMS 2 S promotes the cleavage of S-S bond in aromatic disulfides enabling the synthesis of the corresponding alkyl aryl sulfides through reaction of in situ generated thiosilanes with alkyl carboxylates (Table 1, J). 26 The scope of this reaction has been extended to the synthesis of alkyl aryl selenides from diaryl diselenides. 26 In summary, TMS 2 S has found broad applications as a S1 source in the synthesis of sulfur-containing compounds, from useful building blocks to aromatic heterocycles and thioglycosides.…”

“…26 The scope of this reaction has been extended to the synthesis of alkyl aryl selenides from diaryl diselenides. 26 In summary, TMS 2 S has found broad applications as a S1 source in the synthesis of sulfur-containing compounds, from useful building blocks to aromatic heterocycles and thioglycosides. The recent finding that hexamethyldisilathiane can also promote the cleavage of S-S or Se-Se bonds suggests that the synthetic potential of this reagent has not yet been fully uncovered.…”

“…(H) Copper-catalyzed synthesis of isothiochromenes and benzo[b]thiophenes: 23 • selective 6-endo-dig cyclization • mechanistic studies (I) Generation of thioaldehydes using ionic liquids: 24 • mild conditions • in situ formation of thioaldehydes • one-pot synthesis of 3,6-dihydro-2H-thiopyrans from aryl aldehydes (J) TMS 2 S-promoted cleavage of sulfur-sulfur bond in aromatic disilathianes: 26 • one-pot synthesis of alkyl aryl sulfides • alkyl carboxylates used as alkylation reagents • TMS 2 S not acting as a S1 source but as a promoter of the S-S bond cleavage…”

Disilathiane as a Sulfur Source for the Construction of Isothiochromenes and Benzo[b]thiophenes by Copper-Catalyzed endo-Selective Hydrothiolation

“…13 C NMR (126 MHz, CDCl3):  = 141.0, 140.5, 138.3, 137.6, 137.4, 128.6, 128.4, 128.3, 128.1, 126.6, 126.0, 125.7, 120.5, 114.1, 38.0, 21.2, 14. 2, 140.7, 139.5, 134.3, 128.9, 128.3, 126.5, 124.5, 124.3, 123.5, 122.3, 119.4. 8,141.7,140.8,139.0,130.4 (q,127.5,126.8,126.8,125.9,125.6,124.9,123.1,122.5. Hz, 2 H), 1.73 (quint, J = 7.5 Hz, 2 H), 1.42 (q, J = 7.5 Hz, 2 H), 0.95 (t, J = 7.5 Hz, 3 H).…”

“…The Si-S bonds possess relatively weak bond dissociation energy and the oxophilicity of silicon atom, which allows the use of disilathiane for a variety of useful synthetic transformations, 1 such as thionation of carbonyl compounds, 2 reduction of sulfoxides, 3 nitro compounds, 4 and azides, 5 and diverse C-S bond formations. 6 Our group reported the first transition-metalcatalyzed aryl C-S coupling with 1,1,1,3,3,3hexamethyldisilathiane, 7 and C(sp 3 )-S bond formation between disulfides and alkyl carboxylates via a disilathiane-disulfide interchange reaction, 8 leading to symmetric or unsymmetric sulfides. In addition, disilathianes also play a significant role in construction of sulfur-containing heterocyclic molecules via C-S bond formations to incorporate a sulfur atom into the ring structure.…”