Iron‐Catalyzed Cross‐Coupling Reactions for the Construction of Carbon‐Heteroatom Bonds

Abstract

Carbon-heteroatom bonds are ubiquitous among pesticides, pharmaceutical agents, and natural products. In recent years, significant progress has been made in transition-metal-catalyzed carbon-heteroatom bond formation. Especially, iron-catalyzed reactions have become a focused area in organic chemistry owing to their advantages of low cost, economical and environmental benignity. This review intends to summarize the recent advances in the construction of carbon-heteroatom bonds via cross-coupling reactions using iron as a catalyst, including the formation of CÀ N, CÀ O, CÀ S, CÀ B, and CÀ Si bonds. A series of nucleophilic heteroatoms reagents, reaction classifications, and iron catalytic systems are discussed. In addition, some mechanistic studies have also been described. formation of CÀ N, CÀ O, CÀ S, CÀ B, and CÀ Si bonds are mainly focused. 2. Iron-Catalyzed CÀ N Bond Formation The construction of CÀ N bond by transition metal-catalyzed is one of the most significant transformations in organic synthesis, which is widely employed in chemical, pharmaceutical, and materials industries. [8] The classical method to access CÀ N bond is through the transition metal-catalyzed cross-coupling reaction between aryl or alkenyl halides and amines, also known as Buchwald-Hartwig amination reaction. In recent years, the formation of CÀ N bond via CÀ H activation has been welldocumented. [9] After decades of development, the great progress has been achieved in the transition metals (Cu, Pd, Ni, Fe, Co) catalyzed the construction of the CÀ N bond. [10] However, compared with other transition metals, iron-catalyzed CÀ N bond formation has less been studied, which might be caused by the negative effect of trace metals. [21-22] 2.1. Iron-Catalyzed CspÀ N Bond Formation Alkynamines are essential compounds, widely used in organic reactions such as pericyclic reaction, tandem RCM, Pauson-Khand reaction, Kinugasa reaction, Saucy-Marbet rearrangement, and Ficini-Claisen rearrangement. [11] In 2009, Zhang and coworkers [11e] developed the first example of iron-catalyzed amination of alkynyl bromides (Scheme 1). Nucleophiles such as amide, sulfonamide, and indole could react with alkynyl bromides to obtain alkynamines in high yields under FeCl 3 * 6H 2 O and DMEDA catalytic system. This reaction exhibits good functional group tolerance, and the functional groups

A palladium-catalyzed approach to allenic aromatic ethers and first total synthesis of terricollene A

“…In contrast to the well-established metal-catalyzed coupling reactions between aryl halides and phenols or aliphatic alcohols ( Scheme 1b ), 9 metal-catalyzed coupling reactions of aryl halides and allenols have not been developed ( Scheme 1c ). In a preliminary survey, the palladium- 10 and copper-catalyzed 11 coupling reactions between 4-iodoanisole and allenols were studied; however, only a trace amount of the desired allenyl aryl ether product was obtained ( Scheme 1c , for details, see the ESI ).…”

Recent Metal-Catalyzed Methods for Thioether Synthesis

“…Another earth abundant, low-cost transition metal with low toxicity, which can be utilized as catalyst in C-S cross-couplings is iron. 64 The first iron catalyzed Migita type coupling was published by Bolm and co-workers in 2008 (Scheme 19). 65 Aryl iodides and (hetero)aryl thiols were coupled with FeCl3 as lowcost precatalyst and DMEDA (L8, N,N'-dimethylethylenediamine) as bidentate amine ligand at high temperatures.…”

Copper-Promoted Hiyama Cross-Coupling of Arylsilanes With Thiuram Reagents: A Facile Synthesis of Aryl Dithiocarbamates

“…Transition-metal-catalyzed cross-coupling reactions have been found broad applications for the construction of carbon-carbon and carbon-heteroatom bonds enable the facile preparation of more complex molecules ( Miyaura, 2002 ; Magano and Dunetz, 2011 ; Negishi, 2011 ; Suzuki, 2011 ; Guo and Rueping, 2018 ; Zhang et al, 2020 ). In 1972, Kumada and Tamao ( Tamao et al, 1972 ) reported the cross-coupling reaction of Grignard reagents (RMgX) with organic halides (R’X) catalyzed by nickel/phosphine system.…”