Synthesis of Diiodinated Biphenyls and Iodinated meta‐Terphenyls by Regioselective Suzuki–Miyaura Cross‐Coupling Reactions of 5‐Substituted 1,2,3‐Triiodobenzenes

Abstract

A variety of 2,3-diiodinated biphenyl and iodinated meta-terphenyl derivatives were synthesized by a regioselective Suzuki-Miyaura cross-coupling reaction of 5-substituted 1,2,3triiodobenzenes. By using 1 equiv. of arylboronic acid, the Suzuki-Miyaura reaction yielded 2,3-diiodinated biphenyl derivatives with excellent regioselectivity. The coupling reaction predominantly occurred at the terminal position of the P. O.

Palladium-catalyzed highly regioselective mono and double Sonogashira cross-coupling reactions of 5-substituted-1,2,3-triiodobenzene under ambient conditions

“…Considering the remarkable bioactivities of many 2,3-dihalogenated phenylacetylene derivatives in literature and also to our nding in regioselective Suzuki-Miyaura cross-coupling of 5substituted-1,2,3-triiodobenzene, 19 we felt impelled to examine the Sonogashira cross-couplings on 5-substituted-1,2,3triiodobenzenes aiming forward to diiodinated phenylacetylene derivatives. 5-Substituted-1,2,3-triiodobenzene starting materials were prepared according to our previous procedures from anilines or benzoic acids.…”

“…The use of 2.0 mol equiv. of arylboronic acid under the optimized conditions, 19 provided the trisubstituted derivatives (Scheme 5: 36-37) through one-pot double Suzuki-Miyaura cross-coupling in good isolated yields. It is worth noting that the use of 1.0 mol equiv.…”

Domino C–C/C–O bond formation: palladium-catalyzed regioselective synthesis of 7-iodobenzo[b]furans using 1,2,3-triiodobenzenes and benzylketones

“…In this instance, the first step involved an excellent chemo- and regioselective C–C coupling at the iodo substituent, even in the presence of bromine and/or fluorine substituents, giving the products in good yields. 15 d , e Given the importance of 2,3-diarylbenzo[ b ]furan derivatives in literature, 16 and building on our interest in transformations of 5-substituted-1,2,3-triiodobenzenes, 17 we too were encouraged to develop a new protocol to quickly access this motif. Our goal was to generate densely functionalized benzo[ b ]furan motifs, all with iodine at C-7 to serve as a precursor for further synthetic manipulation.…”

Microwave‐Assisted/Pd‐Catalyzed Domino Synthesis of 2,3,4‐Triiodoanisole from 3‐Anisic Acid: A Superior Substrate for Regioselective Synthesis of 2,3‐Diiodobiphenyls

“…Other methods were also reported for biaryl synthesis under photochemical conditions or via aryl iodonium derivatives . Although palladium‐catalyzed Suzuki‐Miyaura cross‐coupling reaction of aryl halides and arylboronic acids remains one of the mainly used and the most powerful method for accessing biaryl derivatives, 2,3‐diiodinated biaryls remain very limited . This might be explained by the lack of either the availability of polyiodinated arene starting materials or the lack of regioselective and effective tactics to form these derivatives.…”