Iron-Catalyzed Borylation of Aryl Ethers via Cleavage of C–O Bonds

Zeng, Xiaoqin; Zhang, Yuxuan; Liu, Zhengli; Geng, Shasha; He, Yun; Feng, Zhihai

doi:10.1021/acs.orglett.0c00679

Cited by 42 publications

(19 citation statements)

References 66 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Moreover, the mixture of this reaction was monitored by 11 B NMR, and a suspected iron-boron complex 94 was observed ( 11 B NMR, δ = 22; for details, see Supporting Information). On the basis of these preliminary results and our previous studies, 58,59 a mechanism was proposed in Scheme 4. An iron alkoxide ate complex I was obtained through the reaction of t-BuOLi with FeI 2 .…”

Section: Fesupporting

confidence: 51%

“…In our previous work, 58,59 we found that the iron-boronate complex with high reduction potential could promote the borylation of unactivated Csp 2 -O bonds. Inspired by this finding, we envisioned that the iron-boron ate complex might also induce the C-Cl bond cleavage, and this catalytic system could avoid the use of organometallic reagents to produce the low-valent iron species.…”

Section: Resultsmentioning

confidence: 93%

“…32,45,47,48 Therefore, the development of a general, mild, and simple catalytic system for the preparation of tertiary, secondary, and primary alkylboronic esters from alkyl chlorides without the use of organometallic reagents is more attractive. [49][50][51][52][53][54] With our continuing studies on iron catalysis, [55][56][57][58][59][60][61] herein, we describe a general method for the borylation and silylation of tertiary, secondary, and primary unactivated alkyl chlorides through an iron-catalyzed organometallic reagents-free cross-coupling reaction.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Iron-Catalyzed Borylation and Silylation of Unactivated Tertiary, Secondary, and Primary Alkyl Chlorides

et al. 2021

Self Cite

View full text Add to dashboard Cite

Herein, we describe an iron-catalyzed borylation and silylation of unactivated alkyl chlorides, delivering the tertiary, secondary, and primary alkylboronic esters, and secondary, primary alkylsilanes with high efficiency. This protocol exhibits broad substrate scope and good functional group compatibility, allowing the efficient late-stage borylation of biorelevant compounds, thus offering an excellent platform in drug discovery and development. Preliminary mechanistic studies suggest that an alkyl radical was involved in this catalytic system.

show abstract

Section: Fesupporting

confidence: 51%

Section: Resultsmentioning

confidence: 93%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Iron-Catalyzed Borylation and Silylation of Unactivated Tertiary, Secondary, and Primary Alkyl Chlorides

et al. 2021

Self Cite

View full text Add to dashboard Cite

show abstract

“…Recently, the Feng group reported an iron-catalyzed borylation via activation of CÀ N and CÀ O bonds (Scheme 15). [55] Scheme 12. Fe/Cu co-catalyzed borylation of aryl bromides.…”

Section: Iron-catalyzed Csp 2 à B Bond Formationmentioning

confidence: 99%

“…Recently, the Feng group reported an iron‐catalyzed borylation via activation of C−N and C−O bonds (Scheme ) . The inert C−N bond could occur the borylation reaction via iron catalysis, but this transformation proceeded with low efficiency, and only 21% yield of the desired product could be obtained.…”

Section: Iron‐catalyzed C−b Bond Formationmentioning

confidence: 99%

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

et al. 2020

Self Cite

View full text Add to dashboard Cite

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

show abstract

Cobalt‐Catalysed, Ligand‐Controlled Regiodivergent Alkene Hydrosilylation

Docherty

Dominey²,

Thomas

2021

Asian J Org Chem

View full text Add to dashboard Cite

Alkene hydrosilylation is amongst the largest industrial homogenous catalysis processes. Cobalt catalysis offers a sustainable alternative to commonly used platinum catalysts to achieve this transformation. Using two bisiminopyridine cobalt(II) catalysts the regiodivergent hydrosilylation of alkenes has been developed. Variation of pre‐catalyst activator and ligand substituents were investigated to enable the controlled, regiodivergent hydrosilylation of both aryl‐ and alkyl‐substituted alkenes with phenylsilane. In contrast to other regiodivergence strategies, excellent regioselectivity for either isomer was achieved using the same ligand class but differing by a single methyl group (ethyl vs isopropyl).

show abstract

Iron-Catalyzed Borylation of Aryl Ethers via Cleavage of C–O Bonds

Cited by 42 publications

References 66 publications

Iron-Catalyzed Borylation and Silylation of Unactivated Tertiary, Secondary, and Primary Alkyl Chlorides

Iron-Catalyzed Borylation and Silylation of Unactivated Tertiary, Secondary, and Primary Alkyl Chlorides

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

Cobalt‐Catalysed, Ligand‐Controlled Regiodivergent Alkene Hydrosilylation

Contact Info

Product

Resources

About