1,2-Sulfur Migrations

ChemInform Abstract: Copper‐, Silver‐, and Gold‐Catalyzed Migratory Cycloisomerization Leading to Heterocyclic Five‐Membered Rings

“…In 2003, our group discovered that the Cu(I)-catalyzed cycloisomerization of 4-thio-substituted allenone 1 proceeded very efficiently with a 1,2 migration of the phenylsulfanyl group, 37,38 providing 3-thio-substituted furan 39 2 in high yield. 40 This discovery led us to formulate a general concept of transition-metal-catalyzed cascade cycloisomerizations of alkynyl and allenyl systems involving the formal 1,2 migration of different functional groups as the key step in a rapid assembly of densely functionalized heterocyclic cores (vide infra).…”

“…This transformation represents the first example of 1,2 migration of the sulfanyl group from an olefinic sp 2 carbon to an sp center. 37 …”

Tandem 1,2-sulfur migration and (aza)-Diels–Alder reaction of β-thio-α-diazoimines: rhodium catalyzed synthesis of (fused)-polyhydropyridines, and cyclohexenes

“…Particularly, 1,2-sulfur migration in various 1,2-functionalized thio-derivatives is an important tool for the construction of sulfur-containing building blocks and heterocycles. 1 For example, rhodium catalyzed 1,2-sulfur migrations in α-thio carbenes were documented for the synthesis of α-thio-α,β-unsaturated carbonyl compounds 2 and 3-alkoxycarbonyl β-lactam derivatives from β-thio-α-diazo carbonyl compounds. 3 Although 1,2-sulfur migrations in α-thio metalcarbenes have been reported, they are rather limited to only β-thio-α-diazo carbonyl compounds.…”

Construction of Polysubstituted 1,2-Dihydrocyclobuta[b]naphthalenes and 1,2-Dihydrocyclobuta[b]anthracenes with Photoluminescence

“…The R 1 could be an acetoxyl group ( 2, 2l,m), and the yields were satisfactory. The R 2 could be phenyl groups optionally substituted with an electron-withdrawing (Table 2,2a,b,2g,2j,k) or an electron-donating group (Table 2,2c,d,2i). Unfortunately, we failed to obtain target products when R 2 was an alkyl group, indicating that the cyclic intermediates might be stabilized by aryl groups.…”