Cascade C–H Annulation Reaction of Benzaldehydes, Anilines, and Alkynes toward Dibenzo[<i>a</i>,<i>f</i>]quinolizinium Salts: Discovery of Photostable Mitochondrial Trackers at the Nanomolar Level

Kadam, Vilas D.; Feng, Boya; Chen, Xingyu; Liang, Wenbo; Zhou, Fulin; Liu, Yanhong; Gao, Ge; You, Jingsong

doi:10.1021/acs.orglett.8b03015

Cited by 47 publications

(23 citation statements)

References 46 publications

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“…13 C NMR (125 MHz, CDCl3) δ 191.98, 147.24, 139.75, 135.22, 130.30, 129.04, 128.50, 127.72, 127.39. The spectral data matched those reported in the literature(Kadam et al, 2018).4-(Trifluoromethyl)benzoic acid and phenylboronic acid (3d, Figure 3, Entry 4)According to the general procedure, the reaction of 4-(trifluoromethyl)benzoic acid (0.20 mmol), phenylboronic acid (2.0 equiv), Pd(OAc)2 (5 mol%), 1,4-bis(diphenylphosphino)butane (10 mol%), triethylamine (1.5 equiv), H3BO3 (1.5 equiv) and trimethylacetic anhydride (1.5 equiv) in 1,4-dioxane (0.20 M) for 15 h at 160 °C, afforded after work-up and chromatography the title compound in 91% yield (40.5 mg). White solid.…”

supporting

confidence: 83%

Synthesis of Biaryls via Decarbonylative Palladium-Catalyzed Suzuki-Miyaura Cross-Coupling of Carboxylic Acids

Li¹,

Ji²,

Qin³

et al. 2019

iScience

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Summary The biaryl motif is a building block in many drugs, agrochemicals, and materials, and as such it is highly desirable as a synthesis target. The state-of-the-art process for biaryl synthesis from ubiquitous carboxylic acids is decarboxylative cross-coupling involving loss of carbon dioxide (CO 2 ). However, the scope of these methods is severely limited, mainly due to specific substitution required to promote decarboxylation. The present report implements a decarbonylative version with loss of carbon monoxide (CO) that enables to directly engage carboxylic acids in a Suzuki-Miyaura cross-coupling to produce biaryls as a general method with high cross-coupling selectivity using a well-defined Pd(0)/(II) catalytic cycle. This protocol shows a remarkably broad scope (>80 examples) and is performed in the absence of exogenous inorganic bases. In a broader context, the approach shows promise for routine applications in the synthesis of biaryls by carefully controlled decarbonylation of prevalent carboxylic acids.

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supporting

confidence: 83%

Synthesis of Biaryls via Decarbonylative Palladium-Catalyzed Suzuki-Miyaura Cross-Coupling of Carboxylic Acids

Li¹,

Ji²,

Qin³

et al. 2019

iScience

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“…For example, the reaction of p ‐anisaldehyde and p ‐toluidine with diphenylacetylene at 2.5 mol % loading of 2 b and 90 °C in methanol gave the corresponding isoquinolinium salt in 67 % yield, which is comparable with that for the ruthenium catalyst [( p ‐cymene)RuCl 2 ] 2 , [32] the latter working at higher temperature (110 °C in ethanol). In our case, the increase of the reaction temperature to 120 °C in DCE only slightly increases the yield of the target product (to 70 %) [33] . Complex 2 b also exhibited moderate catalytic activity in the reaction of benzamide with two equivalents of diphenylacetylene to form 8H‐isoquinolino[3,2‐a]isoquinolin‐8‐one in 49 % yield via double CH activation [34] .…”

Section: Resultsmentioning

confidence: 63%

“…In our case, the increase of the reaction temperature to 120°C in DCE only slightly increases the yield of the target product (to 70 %). [33] Complex 2 b also exhibited moderate catalytic activity in the reaction of benzamide with two equivalents of diphenylacetylene to form 8H-isoquinolino [3,2-a]isoquinolin-8-one in 49 % yield via double CH activation. [34] At the same time, the reaction of acetanilide with 1-phenyl-1-propyne catalyzed by 2 b gave the corresponding indole derivative in 25 % yield, which is comparable with that for the classical catalyst [Cp*RhCl 2 ] 2 , [35] but lower than for the functionalized indenyl derivative [(η 5 -5-1-(COOEt)-2-Me-3-benzyl-indenyl)RhI 2 ] 2 .…”

Section: Catalytic Activity Of the Halide Complexes 2 Abmentioning

confidence: 99%

Easy Access to Versatile Catalytic Systems for C−H Activation and Reductive Amination Based on Tetrahydrofluorenyl Rhodium(III) Complexes

Kharitonov

Runikhina

Nelyubina

et al. 2021

Chemistry A European J

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On the basis of the 1,2,3,4-tetrahydrofluorenyl ligand, a simple approach was developed to new effective rhodium catalysts for the construction of CÀ C and CÀ N bonds. The halide compounds [(η 5 -tetrahydrofluorenyl)RhX 2 ] 2 (2 a: X = Br; 2 b: X = I) were synthesized by treatment of the bis (ethylene) derivative (η 5 -tetrahydrofluorenyl)Rh(C 2 H 4 ) 2 (1 a) with halogens. An analogous reaction of the cyclooctadiene complex (η 5 -tetrahydrofluorenyl)Rh(cod) (1 b) with I 2 is complicated by the side formation of [(cod)RhI] 2 . The reaction of 2 b with 2,2'-bipyridyl leads to cation [(η 5 -tetrahydrofluorenyl) Rh(2,2'-bipyridyl)I] + (3). The halide abstraction from 2 a,b with thallium or silver salts allowed us to prepare sandwich compounds with incoming cyclopentadienyl, dicarbollide and mesityleneligands [(η 5 -tetrahydrofluorenyl)RhCp] + (4), (η 5 -tet-rahydrofluorenyl)Rh(η-7,8-C 2 B 9 H 11 ) (5), and [(η 5 -tetrahydrofluorenyl)Rh(η-mesitylene)] 2 + (6). The structures of 1 b, 2 b • 2I 2 , 3PF 6 , 4TlI 4 , 5, and [(cod)RhI] 2 were determined by X-ray diffraction. Compounds 2 a,b efficiently catalyze the oxidative coupling of benzoic acids with alkynes to selectively give isocoumarins or naphthalenes, depending on the reaction temperature. Moreover, they showed moderate catalytic activity in other annulations of alkynes with aromatic compounds (such as benzamide, acetanilide, etc.) which proceed through CH activation. Compound 2 b also effectively catalyzes the reductive amination of aldehydes and ketones in the presence of carbon monoxide and water via water-gas shift reaction, giving amines in high yields (67-99 %).

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“…This synergy is probably connected to different influences of each of the precursors on cell physiology, such as the effect of free radicals related to the presence of APS. It is reported that aniline derivatives possess, for example, DNA intercalating properties [19]. However, information on this effect exerted by An or AnH are insufficient.…”

Section: Resultsmentioning

confidence: 99%

Exploring the Critical Factors Limiting Polyaniline Biocompatibility

et al. 2019

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Today, the application of polyaniline in biomedicine is widely discussed. However, information about impurities released from polyaniline and about the cytotoxicity of its precursors aniline, aniline hydrochloride, and ammonium persulfate are scarce. Therefore, cytotoxicity thresholds for the individual precursors and their combinations were determined (MTT assay) and the type of cell death caused by exposition to the precursors was identified using flow-cytometry. Tests on fibroblasts revealed higher cytotoxicity of ammonium persulfate than aniline hydrochloride. Thanks to the synergic effect, both monomers in combination enhanced their cytotoxicities compared with individual substances. Thereafter, cytotoxicity of polyaniline doped with different acids (sulfuric, nitric, phosphoric, hydrochloric, and methanesulfonic) was determined and correlated with impurities present in respective sample (HPLC). The lowest cytotoxicity showed polyaniline doped with phosphoric acid (followed by sulfuric, methanesulfonic, and nitric acid). Cytotoxicity of polyaniline was mainly attributed to the presence of residual ammonium persulfate and low-molecular-weight polar substances. This is crucial information with respect to the purification of polyaniline and production of its cytocompatible form.

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Cascade C–H Annulation Reaction of Benzaldehydes, Anilines, and Alkynes toward Dibenzo[a,f]quinolizinium Salts: Discovery of Photostable Mitochondrial Trackers at the Nanomolar Level

Cited by 47 publications

References 46 publications

Synthesis of Biaryls via Decarbonylative Palladium-Catalyzed Suzuki-Miyaura Cross-Coupling of Carboxylic Acids

Synthesis of Biaryls via Decarbonylative Palladium-Catalyzed Suzuki-Miyaura Cross-Coupling of Carboxylic Acids

Easy Access to Versatile Catalytic Systems for C−H Activation and Reductive Amination Based on Tetrahydrofluorenyl Rhodium(III) Complexes

Exploring the Critical Factors Limiting Polyaniline Biocompatibility

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