Direct formation and reaction of thienyl-based organocopper reagents

Rieke, Reuben D.; Klein, W. R.; Wu, Tse Chong

doi:10.1021/jo00061a024

Cited by 48 publications

(14 citation statements)

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“…IR (neat): 3410, 1640, 910 cm −l ; 1 H NMR (CDCl 3 , 250 MHz): 1.77 (s, 3H), 2.31 (s, 1H), 2.40 (d, The Journal of Organic Chemistry Synthesis of 3-Methyl-1-phenyl-but-3-en-1-one. 43 To a stirred slurry of 3-methyl-1-phenyl-but-3-en-1-ol (7.6 g, 47 mmol) in acetone (100 mL) was added Jones reagent (10 g of chromium trioxide, 10 mL of sulfuric acid, and 30 mL of water) until the color changed to an orangishyellow solution. The solution was filtered and the acetone was removed in vacuo to give a red−brown slurry that was dissolved in diethyl ether (250 mL), and then the ether layer was washed with saturated sodium bicarbonate solution and dried (MgSO 4 ).…”

Section: Methodsmentioning

confidence: 99%

Triplet Sensitized Photolysis of a Vinyl Azide: Direct Detection of a Triplet Vinyl Azide and Nitrene

Rajam

Jadhav

et al. 2014

J. Org. Chem.

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Photolysis of vinylazide 1, which has a built-in acetophenone triplet sensitizer, in argon-saturated toluene results in azirine 2, whereas irradiation in oxygen-saturated toluene yields cyanide derivatives 3 and 4. Laser flash photolysis of azide 1 in argon-saturated acetonitrile shows formation of vinylnitrene 1c, which has a λmax at ∼300 nm and a lifetime of ∼1 ms. Vinylnitrene 1c is formed with a rate constant of 4.25 × 10(5) s(-1) from triplet 1,2-biradical 1b. Laser flash photolysis of 1 in oxygen-saturated acetonitrile results in 1c-O (λmax = 430 nm, τ ≈ 420 μs acetonitrile). Density functional theory (DFT) calculations were used to aid in the characterization of the intermediates formed upon irradiation of azide 1 and to validate the proposed mechanism for its photoreactivity.

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Section: Methodsmentioning

confidence: 99%

Triplet Sensitized Photolysis of a Vinyl Azide: Direct Detection of a Triplet Vinyl Azide and Nitrene

Rajam

Jadhav

et al. 2014

J. Org. Chem.

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“…The crude product is purified by flash chromatography on silica gel eluted with pentane/ether 9/1, yielding 71% of 1-(4-methoxyphenyl)ethanone as a white solid: mp 36 °C, (lit. 23 38-39 °C); 1 H NMR (CDCl3) 24 δ 2.55 (3H, s), 3.85 (3H, s), 6.96 (2H, d, J ) 8.8 Hz), 7.97 (2H, d, J ) 8.8 Hz); 13 C NMR (CDCl3) 24 δ 26.0, 55.0, 113.4 (2C), 130.0, 130.4 (2C), 163.2, 196.2; MS (EI) 24 m/z (relative intensity) 150 (M +• , 48), 135 (100), 107 (6), 92 (7), 77 (30) 19 F NMR (CDCl3) 28 -63.0 (s); MS (EI) m/z (relative intensity) 188 (M + , 3), 173 (100), 145 (52), 125 (6), 95(6), 75(4). Anal.…”

Section: Methodsmentioning

confidence: 99%

Convenient Processes for the Synthesis of Aromatic Ketones from Aryl Bromides and Carboxylic Anhydrides Using a Cobalt Catalysis

et al. 2004

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The cross-coupling of various para- and meta-substituted aromatic bromides, mostly bearing sensitive moieties, with several carboxylic acid anhydrides is reported. This reaction can be carried out in two steps, by forming an aromatic organozinc reagent via cobalt catalysis in the first step, or even more interestingly in a single step, also by using a cobalt-based catalyst. The aromatic ketones are obtained by these new, mild, and convenient methods in 30-79% yields versus starting aryl bromide. Results are also disclosed that suggest the role played by cobalt species in the coupling of organozinc reagents with electrophiles could be similar to those of more commonplace transition metal complexes.

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“…IR (neat): 1737 cm −1 . MS (EI; m/z (relative intensity)): 248 (M + , 1), 205 (12), 203 (21), 115 (14), 101 (64), 88 (100), 83 (22), 73 (41), 70 (47), 60 (45), 57 (27), 55 (68). HRMS (EI): calcd for C 13 H 25 35 ClO 2 (M + ) 248.1543, found 248.1546.…”

Section: Scheme 7 Control Experimentsmentioning

confidence: 99%

Borohydride-Mediated Radical Addition Reactions of Organic Iodides to Electron-Deficient Alkenes

et al. 2014

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Cyanoborohydrides are efficient reagents in the reductive addition reactions of alkyl iodides and electron-deficient olefins. In contrast to using tin reagents, the reaction took place chemoselectively at the carbon-iodine bond but not at the carbon-bromine or carbon-chlorine bond. The reaction system was successfully applied to three-component reactions, including radical carbonylation. The rate constant for the hydrogen abstraction of a primary alkyl radical from tetrabutylammonium cyanoborohydride was estimated to be <1 × 10(4) M(-1) s(-1) at 25 °C by a kinetic competition method. This value is 3 orders of magnitude smaller than that of tributyltin hydride.

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Direct formation and reaction of thienyl-based organocopper reagents

Cited by 48 publications

References 0 publications

Triplet Sensitized Photolysis of a Vinyl Azide: Direct Detection of a Triplet Vinyl Azide and Nitrene

Triplet Sensitized Photolysis of a Vinyl Azide: Direct Detection of a Triplet Vinyl Azide and Nitrene

Convenient Processes for the Synthesis of Aromatic Ketones from Aryl Bromides and Carboxylic Anhydrides Using a Cobalt Catalysis

Borohydride-Mediated Radical Addition Reactions of Organic Iodides to Electron-Deficient Alkenes

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