Palladium-Catalyzed Double-Suzuki–Miyaura Reactions Using Cyclic Dibenziodoniums: Synthesis of o-Tetraaryls

Abstract

Palladium-catalyzed double-Suzuki-Miyaura couplings between cyclic dibenziodoniums and arylboronic acids have been developed. As such, a wide range of o-tetraaryls were synthesized in good to excellent yields of 22-94%. Furthermore, tetraphenylene was prepared in 21% isolated yield with 2,2'-biphenyldiboronic acid by using this method.

Palladium‐Catalyzed Synthesis of Heteroarene‐Fused Cyclooctatetraenes through Dehydrogenative Cyclodimerization

“…[4] Owing to the unique structural and electronic properties of this class of compounds,t here exist potential applications in various fields,i ncluding asymmetric synthesis [5] and supramolecular chemistry. [7] Such ar eaction, however, often gives ac omplicated mixture of oligomers,a nd the desired product is obtained in low to moderate yields.Recently,Pd-catalyzed cyclodimerization of biphenyl derivatives based on Suzuki-Miyaura coupling [8] and Ullman-type coupling [9] (Scheme 1b and c) has emerged as an effective tool for preparing tetraphenylenes.S hi et al [10] and Zhang et al [11] independently developed an ovel reaction system involving the catalytic CÀHf unctionalization [12] of 2iodo-1,1'-biphenyl derivatives (Scheme 1d). [7] Such ar eaction, however, often gives ac omplicated mixture of oligomers,a nd the desired product is obtained in low to moderate yields.Recently,Pd-catalyzed cyclodimerization of biphenyl derivatives based on Suzuki-Miyaura coupling [8] and Ullman-type coupling [9] (Scheme 1b and c) has emerged as an effective tool for preparing tetraphenylenes.S hi et al [10] and Zhang et al [11] independently developed an ovel reaction system involving the catalytic CÀHf unctionalization [12] of 2iodo-1,1'-biphenyl derivatives (Scheme 1d).…”

Atom‐Economical Applications of Diaryliodonium Salts

“…In 2016, Liu and co-workers described the palladium-catalyzed double-Suzuki-Miyaura couplings between cyclic diaryliodonium salts and arylboronic acids for the synthesis of tetraaryl derivatives (Scheme 27). [23] Various ortho-, meta-, or parasubstituted arylboronic acids were well tolerated in this reaction. However,t he heterocyclic arylboronic acids (2-furanylboronic acid and 3-thienylboronic acid) furnished the desired tetraaryl products in moderate yields, and 4-pyridylboronic acid could not afford the desired product at all.Interestingly,2,2'-bi-phenyldiboronic acid couldb ee mployed in the double Suzuki-Miyaura reaction to generate tetraphenylene in 21 % yield.…”

“…In 2016, Liu and co‐workers described the palladium‐catalyzed double‐Suzuki–Miyaura couplings between cyclic diaryliodonium salts and arylboronic acids for the synthesis of tetraaryl derivatives (Scheme ) . Various ortho ‐, meta ‐, or para ‐substituted arylboronic acids were well tolerated in this reaction.…”

Synthesis of tetraphenylene derivatives and their recent advances

“…However, only one example of 1,16-dinitrotetraphenylene was obtained in an extremely low yield of 0.25% [55]. Recently, we employed dibenziodonium salt (92) as a double Suzuki coupling partner and, gratifyingly, 1 was obtained at a 21% isolated yield from 2,2 -biphenyldiboronic acid (Scheme 29) [56]. REVIEW Han et al 903 Besides double Suzuki reactions, Pd-catalyzed Ullmann coupling reactions of diiodobiphenyls in an attempt to construct tetraphenylenes were simultaneously reported by the research groups of Xi and Wong [57,58].…”