Palladium‐Catalyzed Intermolecular Coupling of 2‐Silylaryl Bromides with Alkynes: Synthesis of Benzosiloles and Heteroarene‐Fused Siloles by Catalytic Cleavage of the C(sp³)Si Bond

Selective C–Si Bond Formation through C–H Functionalization

“…Xi and co-workers also reported the [PdCl(π-allyl)] 2 and Pd(PPh 3 ) 4 catalyzed synthesis of benzosiloles by the coupling of 2-silylphenyl bromide and alkynes involving C-Si bond activation (Scheme 53). 46 Similar to their previous report, the addition of an aldehyde (1 equiv) was beneficial. The reaction was compatible with various substituted 2-silylphenyl bromides giving benzosiloles in good yields.…”

“…Inspired form this approach, Xi and co-workers reported the palladium-catalyzed synthesis of benzosilolo[2,3b]indoles by intramolecular coupling of an aryl bromide with an alkylsilane (Scheme 52). 45 Similar to the work by Chatani, 46 the reaction involved Me-Si Bond cleavage followed by intramolecular Ar-Si bond formation.…”

Photocatalyzed cycloaromatization of vinylsilanes with arylsulfonylazides

“…In these regards, arene-fused siloles have especially attracted many concerns due to their promising applications in electronic and optoelectronic devices 9 – 13 . In 2012, Xi 14 and Chatani 15 pioneeringly explored intermolecular coupling-cyclization of alkynes with 2-silylaryl bromides and 2-silylphenylboronic acids to produce 2,3-difunctionalized benzosiloles through Si-C bond cleavage (Fig. 1a ).…”

Versatile telluracycle synthesis via the sequential electrophilic telluration of C(sp2)–Zn and C(sp2)–H bonds

“…A treatment of 3bl with excess n -BuLi in hexane resulted in double tellurium–lithium exchange, 21 and subsequent trapping with Bu 2 SnCl 2 furnished benzostannole 5 in 60% yield. The success of this conversion would hold promise for the use of benzotellurophenes as versatile precursors for different benzoheteroles, 10 such as benzosilole 23 and benzophosphole. 24 …”