53689-84-2Relevant academic research and scientific papers
Aromatization as an Impetus to Harness Ketones for Metallaphotoredox-Catalyzed Benzoylation/Benzylation of (Hetero)arenes
Lee, Shao-Chi,Li, Li-Yun,Tsai, Zong-Nan,Lee, Yi-Hsin,Tsao, Yong-Ting,Huang, Pin-Gong,Cheng, Cheng-Ku,Lin, Heng-Bo,Chen, Ting-Wei,Yang, Chung-Hsin,Chiu, Cheng-Chau,Liao, Hsuan-Hung
, p. 85 - 89 (2022/01/04)
Herein we report ketones as feedstock materials in radical cross-coupling reactions under Ni/photoredox dual catalysis. In this approach, simple condensation first converts ketones into prearomatic intermediates that then act as activated radical sources for cross-coupling with aryl halides. Our strategy enables the direct benzylation/benzoylation of (hetero)arenes under mild reaction conditions with high functional group tolerance.
Mechanochemical Solvent-Free Suzuki–Miyaura Cross-Coupling of Amides via Highly Chemoselective N?C Cleavage
Ma, Yangmin,Shao, Lei,Szostak, Michal,Wang, Ruihong,Zhang, Jin,Zhang, Pei
supporting information, (2022/01/04)
Although cross-coupling reactions of amides by selective N?C cleavage are one of the most powerful and burgeoning areas in organic synthesis due to the ubiquity of amide bonds, the development of mechanochemical, solid-state methods remains a major challe
Self-Assembled 2,3-Dicyanopyrazino Phenanthrene Aggregates as a Visible-Light Photocatalyst
He, Min,Yu, Xiaoqiang,Wang, Yi,Li, Fei,Bao, Ming
, p. 5016 - 5025 (2021/04/12)
In this study, 2,3-dicyanopyrazino phenanthrene (DCPP), a commodity chemical that can be prepared at an industrial scale, was used as a photocatalyst in lieu of Ru or Ir complexes in C-X (X = C, N, and O) bond-forming reactions under visible-light irradiation. In these reactions, [DCPP]n aggregates were formed in situ through physical π-πstacking of DCPP monomers in organic solvents. These aggregates exhibited excellent photo- and electrochemical properties, including a visible light response (430 nm), long excited-state lifetime (19.3 μs), high excited-state reduction potential (Ered([DCPP]n*/[DCPP]n·-) = +2.10 V vs SCE), and good reduction stability. The applications of [DCPP]n aggregates as a versatile visible-light photocatalyst were demonstrated in decarboxylative C-C cross-coupling, amidation, and esterification reactions.
Synthesis of biaryl ketones and biaryl diketones via carbonylative Suzuki-Miyaura coupling reactions catalyzed by bridged bis(N-heterocyclic carbene)palladium(II) catalysts
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Page/Page column 20; 25-28, (2021/12/23)
This disclosure relates to bridged bis(N-heterocyclic carbene)palladium(II) complexes, methods of preparing the complexes, and methods of using the complexes in Suzuki-Miyaura coupling reactions.
Pd-Catalysed carbonylative Suzuki-Miyaura cross-couplings using Fe(CO)5under mild conditions: generation of a highly active, recyclable and scalable ‘Pd-Fe’ nanocatalyst
Zhu, Zhuangli,Wang, Zhenhua,Jian, Yajun,Sun, Huaming,Zhang, Guofang,Lynam, Jason M.,McElroy, C. Robert,Burden, Thomas J.,Inight, Rebecca L.,Fairlamb, Ian J. S.,Zhang, Weiqiang,Gao, Ziwei
supporting information, p. 920 - 926 (2021/02/09)
The dual function and role of iron(0) pentacarbonyl [Fe(CO)5] has been identified in gaseous CO-free carbonylative Suzuki-Miyaura cross-couplings, in which Fe(CO)5supplied COin situ, leading to the propagation of catalytically active Pd-Fe nanoparticles. Compared with typical carbonylative reaction conditions, CO gas (at high pressures), specialised exogenous ligands and inert reaction conditions were avoided. Our developed reaction conditions are mild, do not require specialised CO high pressure equipment, and exhibit wide functional group tolerance, giving a library of biaryl ketones in good yields.
Photoinduced Acetylation of Anilines under Aqueous and Catalyst-Free Conditions
Yang, Yu-Ming,Yan, Wei,Hu, Han-Wei,Luo, Yimin,Tang, Zhen-Yu,Luo, Zhuangzhu
, p. 12344 - 12353 (2021/09/02)
A green and efficient visible-light induced functionalization of anilines under mild conditions has been reported. Utilizing nontoxic, cost-effective, and water-soluble diacetyl as photosensitizer and acetylating reagent, and water as the solvent, a variety of anilines were converted into the corresponding aryl ketones, iodides, and bromides. With advantages of environmentally friendly conditions, simple operation, broad substrate scope, and functional group tolerance, this reaction represents a valuable method in organic synthesis.
Evaluation of Cyclic Amides as Activating Groups in N-C Bond Cross-Coupling: Discovery of N-Acyl-δ-valerolactams as Effective Twisted Amide Precursors for Cross-Coupling Reactions
Bisz, Elwira,Chen, Hao,Dziuk, B?a?ej,Ejsmont, Krzysztof,Lalancette, Roger,Pyle, Daniel J.,Rahman, Md. Mahbubur,Szostak, Michal,Szostak, Roman,Wang, Qi
, p. 10455 - 10466 (2021/07/31)
The development of efficient methods for facilitating N-C(O) bond activation in amides is an important objective in organic synthesis that permits the manipulation of the traditionally unreactive amide bonds. Herein, we report a comparative evaluation of a series of cyclic amides as activating groups in amide N-C(O) bond cross-coupling. Evaluation of N-acyl-imides, N-acyl-lactams, and N-acyl-oxazolidinones bearing five- and six-membered rings using Pd(II)-NHC and Pd-phosphine systems reveals the relative reactivity order of N-activating groups in Suzuki-Miyaura cross-coupling. The reactivity of activated phenolic esters and thioesters is evaluated for comparison in O-C(O) and S-C(O) cross-coupling under the same reaction conditions. Most notably, the study reveals N-acyl-δ-valerolactams as a highly effective class of mono-N-acyl-activated amide precursors in cross-coupling. The X-ray structure of the model N-acyl-δ-valerolactam is characterized by an additive Winkler-Dunitz distortion parameter ?(τ+χN) of 54.0°, placing this amide in a medium distortion range of twisted amides. Computational studies provide insight into the structural and energetic parameters of the amide bond, including amidic resonance, N/O-protonation aptitude, and the rotational barrier around the N-C(O) axis. This class of N-acyl-lactams will be a valuable addition to the growing portfolio of amide electrophiles for cross-coupling reactions by acyl-metal intermediates.
Suzuki coupling of aroyl-MIDA boronate esters – A preliminary report on scope and limitations
Lai, Samson,Lin, Wen Xuan,Perrin, David M.,Takaesu, Noah
, (2021/05/31)
Recent methodological reports for synthesizing acyl-MIDA boronate esters compel an investigation of their potential use as substrates in a standard Suzuki-Miyaura cross-coupling reaction. Here we report the production of benzophenones by C[sbnd]C cross coupling between a benzoyl-MIDA boronate ester and a multitude of aryl bromide substrates in adequate yields following optimization under ambient conditions outside of a glove box. Under these standard conditions, none of several acyl-MIDA boronate esters (in an alkyl series) serves as a competent coupling partner. The substrate scope is also limited by the finding that the corresponding trifluoroborates of both acyl- and aroyltrifluroborates are not suitable substrates. For reasons of availability and synthetic difficulty in procuring other aroyl-MIDA boronates, this preliminary study examines the reactivity of benzoyl-MIDA boronate with several aryl bromide substrates.
Selective electrochemical oxidation of aromatic hydrocarbons and preparation of mono/multi-carbonyl compounds
Li, Zhibin,Zhang, Yan,Li, Kuiliang,Zhou, Zhenghong,Zha, Zhenggen,Wang, Zhiyong
, p. 2134 - 2141 (2021/09/29)
A selective electrochemical oxidation was developed under mild condition. Various mono-carbonyl and multi-carbonyl compounds can be prepared from different aromatic hydrocarbons with moderate to excellent yield and selectivity by virtue of this electrochemical oxidation. The produced carbonyl compounds can be further transformed into α-ketoamides, homoallylic alcohols and oximes in a one-pot reaction. In particular, a series of α-ketoamides were prepared in a one-pot continuous electrolysis. Mechanistic studies showed that 2,2,2-trifluoroethan-1-ol (TFE) can interact with catalyst species and generate the corresponding hydrogen-bonding complex to enhance the electrochemical oxidation performance. [Figure not available: see fulltext.]
Novel and efficient bridged bis(N-heterocyclic carbene)palladium(II) catalysts for selective carbonylative Suzuki–Miyaura coupling reactions to biaryl ketones and biaryl diketones
El Ali, Bassam,Fettouhi, Mohammed,Mansour, Waseem
, (2020/03/23)
Bridged N,N′-substituted bisbenzimidazolium bromide salts (L1, L2, and L3) were synthesized and fully characterized. Reactions of palladium acetate with L1, L2, and L3 afforded corresponding new bridged bis(N-heterocyclic carbene)palladium(II) complexes (C1, C2, and C3) in high yields. The X-ray structure of complex C1 showed that the Pd(II) ion is bonded to the two carbon atoms of the bis(N-heterocyclic carbene) and two bromido ligands are in the cis position, resulting in a distorted square planar geometry. The three Pd(NHC)2Br2 complexes C1, C2, and C3 were evaluated in carbonylative Suzuki–Miyaura coupling reactions of aryl boronic acids with aryl halides and displayed high catalytic activity with low catalyst loading. The coupling reactions of aryl bromides were selective towards the carbonylation product at higher carbon monoxide pressure.
