CuI-Catalyzed Ullmann-Type Coupling of Phenols and Thiophenols with 5-Substituted 1,2,3-Triiodobenzenes: Facile Synthesis of Mammary Carcinoma Inhibitor BTO-956 in One Step

Abstract

A facile and unprecedented synthesis of 2,3-diiodinated or 2,6-diiodinated diarylether/thioether derivatives through regioselective Ullmann-type cross couplings of 5-substituted-1,2,3-triiodobenzene and phenols/thiophenols is described. Remarkably, the coupling reactions are simply controlled by the type of nucleophiles and the nature of C5 substituent at 1,2,3-triiodoarenes providing the internal or terminal coupling products in high regioselectivity and good isolated yields. Noticeable steric and electronic effects were clearly observed on both 1,2,3-triiodoarene and nucleophile. The highest yields were isolated from a combination between either electron-poor 1,2,3-triiodoarenes and phenols or electron-rich 1,2,3-triiodoarenes and thiophenols. The optimized conditions were found to be suitable for several functional groups. Using this methodology, mammary carcinoma inhibitor BTO-956 is prepared in only one step with excellent regioselectivity and good isolated yield. This report discloses the first method to make 2,3-diiodinated and 2,6-diiodinated diarylethers/thioethers in one step that is efficient, regioselective, general in scope and truly remarkable precursors for other transformations.

Fe3O4 supported [Cu(ii)(met)(pro-H)2] complex as a novel nanomagnetic catalytic system for room temperature C–O coupling reactions

“…Numerous procedures using various reagents have been described so far for the Ullmann synthesis of diaryl ethers. [25][26][27] In this sense, homogeneous copper-mediated methods have attracted interesting attention. [28][29][30] Heretofore, various reducing agents have been utilized as an electron source to activate the Cu species.…”

Immobilization of PdCl2 on a Natural Asphalt Sulfonic Acid Network for C−N and C−O bonds Formation

“…Transition-metal-catalyzed formation of CÀ N and CÀ O bonds by cross-coupling reactions is a powerful tool for the preparation of numerous important products in pharmaceutical, biological and agrochemicals products. [8][9][10] Cross-couplings, such as the CÀ N [11][12][13] and CÀ O [14][15][16][17] coupling reactions, are currently regarded as the most versatile and useful tools to perform organic syntheses both in industrial production and academic laboratories. Palladium is one of the powerful metals for coupling reactions.…”