Synthesis of 1,4-diaryl-2-naphthoates based on site-selective Suzuki–Miyaura reactions

Site-selective Suzuki–Miyaura coupling of heteroaryl halides – understanding the trends for pharmaceutically important classes

“…Langer et al have proposed that this is consistent with the naphthalene having significant diene character and being relatively easily polarised in its substituted ring thus allowing the ester substituent to impart greater electrophilicity to the proximal C1 position than is possible for the phenyl system without incurring a concomitant energetic penalty from loss of aromaticity. 38 Langer has studied several additional ditriflate-containing substrates in a systematic fashion and similar conclusions regarding the delicate balance of steric vs. electronic factors emerge. 13…”

“…The divergent behaviour of methyl 1,4-ditrifloxy phenyl-2-carboxylate ( 21 ) 37 and phenyl 1,4-ditrifloxynaphthalene-2-carboxylate ( 23 ) 38 with respect to their SMC site-selectivity is also revealing. Although not heteroarenes, a comparison of their behaviour demonstrates how the subtle interplay between steric and electronic effects imparted by a substituent can be critical in controlling SMC reactions when intrinsic ring polarity effects are weak ( Scheme 4 ).…”

Site‐Selective Suzuki–Miyaura and Sonogashira Cross Coupling Reactions of the Bis(triflate) of 2,4′‐Bis(hydroxy)diphenyl Sulfone

“…Similar conditions were previously used in Suzuki reactions of related bis(triflates). [22] The use of potassium phosphate (K 3 PO 4 ) as the base and 1,4-dioxane (110 8C, 4 h) gave optimal yields. The best yield was obtained for the reaction of simple phenylboronic acid.…”

“…The first attack usually occurs at the electronically more deficient or sterically less hindered position. [20][21][22] Recently, we reported [23] the synthesis of bis(diaryl) sulfones by site-selective Suzuki-Miyaura reactions of the bis(triflate) of 2,4'-bis(dihydroxy)diphenyl sulfone. Herein, we report full details of these studies.…”

Synthesis of 1,2-Diarylnaphthalenes by Chemoselective Suzuki-Miyaura Reactions of 2-Bromo-1-(trifluoromethanesulfonyloxy)naphthalene

“…Recently, we have reported regioselective palladium-catalyzed Suzuki crosscoupling reactions of the bis(triflate) of phenyl 1,4-dihydroxy-2-naphthoate. 11 Herein, we wish to report what are, to the best of our knowledge, the first Suzuki-Miyaura reactions of 2-bromo-1-(trifluoromethanesulfonyloxy)naphthalene. These reactions proceed with excellent chemoselectivity and provide a convenient approach to various arylated naphthalene derivatives which are not readily available by other methods.…”