Expanding the Diversity of Polycyclic Aromatics Through a Suzuki–Miyaura Cross‐Coupling Strategy

Abstract

In recent years, Pd‐catalyzed Suzuki–Miyaura (SM) cross‐coupling reactions have revolutionized approaches to carbon–carbon bond formation. We have studied the application of SM coupling with several (ca. 16) complex molecular structures of particular relevance to scientists working at the interfaces of chemistry, biology, and materials sciences. In this regard, various structurally or biologically important polycyclic molecules (e.g., benzocrowns, C3‐symmetric molecules, 9,10‐disubstituted anthracenes, and sulfones) and unusual amino acid derivatives have been modified by this reaction, while it has also been shown that allylation of aromatics through the use of a commercially available boronic acid ester by SM coupling under CsF/Pd0 conditions is feasible. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

Synthesis of New N‐Ethyl Dehydroamino Acid Derivatives: N‐Ethyl β,β‐Dibromo, N‐Ethyl β‐Bromo β‐Substituted, and N‐Ethyl β,β‐Disubstituted N‐Protected Dehydroamino Acid Methyl Esters

“…Methyl Esters of N ‐Protected β‐Bromo Dehydroamino Acids: Z(NO 2 )‐ΔAla(β,β‐Br)‐OMe ( 4a ),18 Z‐ΔAla(β,β‐Br)‐OMe ( 4b ),18 Boc‐ΔAla(β,β‐Br)‐OMe ( 4c ),20a 2‐Fur‐ΔAla(β,β‐Br)‐OMe ( 4d ),23 Bz(4‐OMe)‐ΔAla(β,β‐Br)‐OMe ( 4e ),23 Z(NO 2 ) ‐ E ‐ΔAbu(β‐Br)‐OMe ( E ‐5a ),18 Z(NO 2 )‐ Z ‐ΔAbu(β‐Br)‐OMe ( Z ‐5a ),18 Z‐ Z ‐ΔAbu‐(β‐Br)OMe ( Z ‐5b ),18 Boc‐ Z ‐ΔAbu(β‐Br)‐OMe ( Z ‐5c ),24 Tos‐ Z ‐ΔAbu(β‐Br)‐OMe ( Z ‐5g ),18 Boc‐ Z ‐ΔPhe(β‐Br)‐Ome ( Z ‐6c ),20b Tos‐ Z ‐ΔPhe(β‐Br)‐OMe ( Z ‐6g );18 the syntheses of these compounds have been described previously.…”

Palladium complexes of amido-functionalized N-heterocyclic carbenes as effective precatalysts for the Suzuki–Miyaura C–C cross-coupling reactions of aryl bromides and iodides

“…40 mL) was stirred at room temperature for 4 h. The reaction mixture was filtered, and the solvent was removed under vacuum to give the product 2b as a white solid (2.89 g, 61%). 1 2 Ag} + Cl À (0.471 g, 0.625 mmol) and (COD)PdCl 2 (0.178 g, 0.625 mmol) was dissolved in CH 2 Cl 2 (ca. 40 mL) and was stirred at room temperature for 6 h, at which the point the formation of an off-white AgCl precipitate was observed.…”

“…As a convenient approach to accessing the ''biaryl frameworks", so ubiquitous in many important bioactive molecules as well as in value-added chemical feedstock, the Suzuki-Miyaura C-C crosscoupling reaction, today, has emerged as a major work horse in synthetic organic chemistry [1][2][3][4][5][6][7]. In particular, the famed reaction involves highly efficient C-C cross-coupling of aryl halide with aryl boronic acid in a catalytic fashion aided by palladium in presence of a base.…”

Palladium‐catalysed room‐temperature Suzuki–Miyaura coupling in water extract of pomegranate ash, a bio‐derived sustainable and renewable medium

“…Suzuki–Miyaura cross‐coupling (SMC) serves as a unique and versatile tool in making carbon–carbon bonds, especially in biaryl synthesis . Biaryls and their heteroatom analogues are among the most important structural features of biologically active natural products, pharmaceuticals and agrochemicals .…”