Copper(I)-Promoted Synthesis of Chloromethyl Ketones from Trichloromethyl Carbinols

Ram, Ram N.; Manoj, T. P.

doi:10.1021/jo8007644

Cited by 35 publications

(23 citation statements)

References 54 publications

(27 reference statements)

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“…PPNCl was purchased from Aldrich and stored in an Ar‐filled glove box. ortho ‐anisaldehyde was prepared by methylation of salicylaldehyde according to a previously published procedure 32…”

Section: Methodsmentioning

confidence: 99%

Copolymerisation of Propylene Oxide and Carbon Dioxide by Dinuclear Cobalt Porphyrins

et al. 2013

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Two dinuclear cobalt porphyrins comprising different structural tethering motifs at the porphyrin periphery were synthesised, along with a representative mononuclear cobalt porphyrin, and their catalytic activities tested towards carbon dioxide–propylene oxide copolymerisation in the presence of bis(triphenylphosphoranyl)ammonium chloride cocatalyst. The catalytic activities of the mononuclear and the bis‐para‐tethered dinuclear cobalt porphyrin with selective formation of poly(propylene carbonate) are largely comparable, showing no benefit of dinuclearity in contrast to the case of cobalt salen complexes and suggesting that polymer growth proceeds exclusively from one metal centre. The alternative bis‐ortho‐tethered porphyrin demonstrated considerably reduced activity, with dominant formation of cyclic propylene carbonate, as a result of hindered substrate approach at the metal centre. Time‐resolved UV/Vis spectroscopic studies suggested a general intolerance of the cobalt(III) porphyrin catalysts towards the copolymerisation conditions in the absence of carbon dioxide pressure, leading to catalytically inactive cobalt(II) species. In the presence of carbon dioxide, the bis‐ortho‐tethered catalyst showed the fastest deactivation, which is related to an unfavourable steric arrangement of the linker fragment, as was also confirmed by NMR spectroscopic measurements.

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Section: Methodsmentioning

confidence: 99%

Copolymerisation of Propylene Oxide and Carbon Dioxide by Dinuclear Cobalt Porphyrins

et al. 2013

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“…2‐Chloro‐1‐( p ‐tolyl)ethanone (2z): 15 Colorless solid (27.3 mg, 92 %). 1 H NMR (400 MHz, CDCl 3 ): δ = 7.85 (d, J = 8.0 Hz, 2 H), 7.29 (t, J = 8.0 Hz, 2 H), 4.68 (s, 2 H), 2.42 (s, 3 H) ppm.…”

Section: Methodsmentioning

confidence: 99%

First Catalyzed Hydration of Haloalkynes by a Recyclable Catalytic System

Zou

Dong

et al. 2015

Eur J Org Chem

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The hydration of haloalkynes to give α‐halomethyl ketones was achieved based on a combination of a Cu(OAc)2 catalyst and a TFA (trifluoroacetic acid) promoter. This is the first synthesis of chloro/bromo/iodo methyl ketones through a hydration reaction catalyzed by a recyclable catalytic system. The catalytic system has a wide substrate scope and excellent chemoselectivity, and the procedure can also be scaled up.

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“…Starting materials 1a-f were prepared by the bromination of the corresponding acetophenones. 37 2-Iodoacetylfuran 1g and 1-iodo-2-octanone 1h were prepared from 2-chloroacetylfuran 38 and 1-chloro-2-octanone, 38 respectively. 1i was commercially available and 1j-l were prepared by the bromoacetylation of amines using bromoacetylbromide in DCM at 0-25 ˚C.…”

Section: Methodsmentioning

confidence: 99%

Synthesis of α-Functionalized Trichloromethylcarbinols

Ram

Soni

2015

J. Org. Chem.

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A new series of α-functionalized trichloromethylcarbinols have been synthesized from corresponding α-halomethyl ketones, esters, and amides in 48-78% overall yields. Reactivity of nitrates obtained in the first step was dependent on the electron-withdrawing nature of the functional groups, and increases with increasing electron deficiency. Synthetic applications of such trichloromethylcarbinols for the preparation of chloromethyl-α-diketones, trichloromethylated dihydrofurans, and enol acetates of α-functionalized acid chlorides have been demonstrated. The reaction of these compounds in the Jocic-Reeve reaction was also demonstrated.

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Copper(I)-Promoted Synthesis of Chloromethyl Ketones from Trichloromethyl Carbinols

Abstract: Reaction of several trichloromethyl carbinols with 2 equiv of CuCl/bpy in refluxing DCE for 3 h afforded chloromethyl ketones in excellent yield by 1,2-H shift in the copper-chlorocarbenoid intermediate.

Cited by 35 publications

References 54 publications

Copolymerisation of Propylene Oxide and Carbon Dioxide by Dinuclear Cobalt Porphyrins

Copolymerisation of Propylene Oxide and Carbon Dioxide by Dinuclear Cobalt Porphyrins

First Catalyzed Hydration of Haloalkynes by a Recyclable Catalytic System

Synthesis of α-Functionalized Trichloromethylcarbinols

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Copper(I)-Promoted Synthesis of Chloromethyl Ketones from Trichloromethyl Carbinols

Abstract: Reaction of several trichloromethyl carbinols with 2 equiv of CuCl/bpy in refluxing DCE for 3 h afforded chloromethyl ketones in excellent yield by 1,2-H shift in the copper-chlorocarbenoid intermediate.

Cited by 35 publications

References 54 publications

Copolymerisation of Propylene Oxide and Carbon Dioxide by Dinuclear Cobalt Porphyrins

Copolymerisation of Propylene Oxide and Carbon Dioxide by Dinuclear Cobalt Porphyrins

First Catalyzed Hydration of Halo­alkynes by a Recyclable Catalytic ­System

Synthesis of α-Functionalized Trichloromethylcarbinols

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First Catalyzed Hydration of Haloalkynes by a Recyclable Catalytic System