Cuprous trimethylsilylacetylide. Preparation and reaction with acid chlorides

Logue, Marshall W.; Moore, Gary L.

doi:10.1021/jo00889a038

Cited by 66 publications

(19 citation statements)

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“…The reaction of 1‐phenyl‐3‐trimethylsilanylprop‐2‐yn‐1‐ol (201.8 mg, 1.0 mmol), Fe(NO 3 ) 3 ⋅9 H 2 O (20.8 mg, 0.05 mmol), TEMPO (8.1 mg, 0.05 mmol) and NaCl (3.0 mg, 0.05 mmol) in DCE (5 mL) afforded 1‐phenyl‐3‐(trimethylsilyl)propynone40 as an oil; yield: 183.5 mg (92%) (petroleum ether/diethyl ether=20/1); 1 H NMR (300 MHz, CDCl 3 ): δ =8.14 (d, J =8.1 Hz, 2 H), 7.61 (t, J =7.4 Hz, 1 H), 7.48 (t, J =7.7 Hz, 2 H), 0.32 (s, 9 H); 13 C NMR (75.4 MHz, CDCl 3 ): δ =177.64, 136.48, 134.11, 129.60, 128.54, 100.84, 100.49, −0.73; IR (neat): ν =2153, 1643, 1598, 1579, 1450, 1312, 1243, 1173, 1035, 1016 cm −1 ; MS (EI): m/z =202 (M + , 16.37), 187 (100).…”

Section: Methodsmentioning

confidence: 99%

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Development of a General and Practical Iron Nitrate/TEMPO‐Catalyzed Aerobic Oxidation of Alcohols to Aldehydes/Ketones: Catalysis with Table Salt

et al. 2011

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Oxidation of alcohols is a fundamental transformation related to our daily life. Traditional approaches with at least one stoichiometric amount of oxidants are expensive and cause serious environmental burdens. There are many reports on the aerobic oxidation of simple alcohols such as alkyl or phenyl carbinols and allylic alcohols, which used oxygen or air as the environmentally benign oxidant forming water as the only by-product. However, no such protocol has been reported for allenols and propargylic alcohols. Thus, it still highly desirable to develop efficient room temperature oxidations of alcohols with a wide scope including allenols and propargylic alcohols. In this paper, an efficient and clean aerobic oxidation of so far the widest spectrum of alcohols using 1 atm of oxygen or air, producing aldehydes/ketones at room temperature in fairly high isolated yields mostly within a couple of hours is described. It is interesting to observe that the reaction has been efficiently expedited by a catalytic amount of sodium chloride in easily recoverable 1,2-dichloroethane. A mechanism involving NO and NO 2 has been proposed based on the results of the control experiments and GC-MS studies of the in-situ formed gas phase of the reaction mixture.

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Section: Methodsmentioning

confidence: 99%

“…The reaction of 1‐phenyl‐3‐trimethylsilanylprop‐2‐yn‐1‐ol (200.6 mg, 1.0 mmol), Fe(NO 3 ) 3 ⋅9 H 2 O (21.9 mg, 0.05 mmol), TEMPO (4.7 mg, 0.03 mmol) and NaCl (3.2 mg, 0.05 mmol) in DCE (5 mL) afforded 1‐phenyl‐3‐(trimethylsilyl)propynone40 as an oil; yield: 185.5 mg (93%) (petroleum ether/diethyl ether=20/1).…”

Section: Methodsmentioning

confidence: 99%

Development of a General and Practical Iron Nitrate/TEMPO‐Catalyzed Aerobic Oxidation of Alcohols to Aldehydes/Ketones: Catalysis with Table Salt

et al. 2011

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“…Elemental analyses were performed by the ''Service Central d'Analyses du CNRS'', Vernaison, France and CRMPO, Rennes, France. The synthesis of cis-[(dppe) 2 RuCl 2 ] (1), [41] 2a, and 2b, [42] 1-phenyl-3-trimethylsilylpropynone, [43] 1,2-dibenzoylacetylene, [44] and of propargyl alcohols 3aϪb [25] were performed by using literature methods. Compounds 3cϪd, [45] 8, [46] and 13 [47] , reported in this section, were previously described.…”

Section: Methodsmentioning

confidence: 99%

Carbon‐Rich Ruthenium Complexes Containing Bis(allenylidene) and Mixed Alkynyl−Allenylidene Bridges

et al. 2005

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The cover picture shows two examples of stable polynuclear ruthenium systems containing delocalized carbon-rich bridges with unusual topologies. In this work, the synthesis, the spectroscopic and voltammetric studies of a new family of bis(allenylidene) and mixed allenylideneϪacetylide complexes are presented. The nature of the reduced species, which are mainly ligand-centered, is pointed out by means of ESR and IR spectroscopy. The UV/Vis and electrochemical studies show the large influence of the bridge on the electronic interaction between the redox centers and the fine tuning of this property. These new conjugated molecules appear to be promising alternatives to the classical bis(acetylide) systems for the construction of metal-containing unsaturated oligomers or polymers to mediate electron-transfer processes. Details are discussed in the article by S. Rigaut, D. Touchard et al. on p. 447 ff.

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“…The reaction of metal 12,13 and metalloid 14 acetylides with acyl chlorides is one common route for the preparation of ynones. Alternatively, the synthesis of ynones from acyl chloride can be achieved via two-step procedures using Weinreb amides and organolithium or Grignard reagents.…”

Section: Introductionmentioning

confidence: 99%

Metal-Free Synthesis of Ynones from Acyl Chlorides and Potassium Alkynyltrifluoroborate Salts

Taylor

Bolshan

2013

Org. Lett.

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Ynones are a valuable functional group and building block in organic synthesis. Ynones serve as a precursor to many important organic functional groups and scaffolds. Traditional methods for the preparation of ynones are associated with drawbacks including harsh conditions, multiple purification steps, and the presence of unwanted byproducts. An alternative method for the straightforward preparation of ynones from acyl chlorides and potassium alkynyltrifluoroborate salts is described herein. The adoption of organotrifluoroborate salts as an alternative to organometallic reagents for the formation of new carbon-carbon bonds has a number of advantages. Potassium organotrifluoroborate salts are shelf stable, have good functional group tolerance, low toxicity, and a wide variety are straightforward to prepare. The title reaction proceeds rapidly at ambient temperature in the presence of a Lewis acid without the exclusion of air and moisture. Fair to excellent yields may be obtained via reaction of various aryl and alkyl acid chlorides with alkynyltrifluoroborate salts in the presence of boron trichloride. Video LinkThe video component of this article can be found at

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Cuprous trimethylsilylacetylide. Preparation and reaction with acid chlorides

Cited by 66 publications

References 1 publication

Development of a General and Practical Iron Nitrate/TEMPO‐Catalyzed Aerobic Oxidation of Alcohols to Aldehydes/Ketones: Catalysis with Table Salt

Development of a General and Practical Iron Nitrate/TEMPO‐Catalyzed Aerobic Oxidation of Alcohols to Aldehydes/Ketones: Catalysis with Table Salt

Carbon‐Rich Ruthenium Complexes Containing Bis(allenylidene) and Mixed Alkynyl−Allenylidene Bridges

Metal-Free Synthesis of Ynones from Acyl Chlorides and Potassium Alkynyltrifluoroborate Salts

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