Kinetic studies and improved reaction conditions for the halogen shift rearrangments of aryldihalopropanols

Jensen, Bruce L.; Burke, Scott E.; Thomas, Susan E.

doi:10.1016/0040-4020(78)80194-x

Cited by 5 publications

(2 citation statements)

References 11 publications

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“…The related enolates 8 b and 8 c , featuring Me substitution at one or the two olefinic sites of 8 a can be prepared by the same methodology (Scheme a). The chloroaryl precursors needed for these syntheses are not commercially available, but are obtained by the reaction of 2‐chlorobenzonitrile with the appropriate Grignard reagent, followed by acid hydrolysis of the resulting imine 14. Their oxidative addition to [Ni(cod) 2 ] in the presence of dippe (45 °C, 24 h) yields the expected nickel ortho ‐substituted aryls 6 b and 6 c , as orange crystalline solids, with spectroscopic properties similar to those of 6 a .…”

Section: Resultsmentioning

confidence: 99%

Cyclic Enolates of Ni and Pd: Equilibrium between C‐ and O‐Bound Tautomers and Reactivity Studies

Cámpora¹,

Maya²,

Carmona³

et al. 2005

Chemistry A European J

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2-acylaryl complexes of Ni and Pd containing chelating diphosphines react with KtBuO to give metallacyclic enolate complexes. While coordination through the carbon atom is preferred in the case of Pd, the nickel O-enolate compounds are formed as the corresponding O-tautomers. Slow equilibration between O- and C-enolate tautomers is observed for the nickel complex with an unsubstituted enolate function (M-O-C=CH(2)). Theoretical DFT calculations suggest that the barrier for the tautomer exchange has its origin in the rigidity of the metallacycle. Whilst the C-enolate tautomer is unreactive towards aldehydes, the corresponding O-enolate adds to MeCHO and PhCHO, giving rise to products that retain the enolate functionality. The carbonylation of these products cleanly leads to the formation of enol lactones in a highly selective manner.

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Section: Resultsmentioning

confidence: 99%

Cyclic Enolates of Ni and Pd: Equilibrium between C‐ and O‐Bound Tautomers and Reactivity Studies

Cámpora¹,

Maya²,

Carmona³

et al. 2005

Chemistry A European J

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“…with an excess of bromine in carbon tetrachloride gives 2,4,6-tribromo-3-bromomethyl-(125) and 2,6,6-tribromo-3-dibromomethyl-5,5-dimethyl-2-cyclohexenone (126), respectively at 0 and 25°C. Further treatment of 125 affords the pentabmmocyclohexenone (127) (equation 80)2"2.…”

Section: Ph'mentioning

confidence: 99%

Synthesis and reactivity ofα-halogenated ketones

Kimpe¹,

Verh²

Halides, Pseudo-Halides and Azides: Vol. 1 (1983)

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Rearrangement of 1‐aryl‐2,2‐Dichloro‐1‐Alkanones and 1‐Aryl‐2,2‐Dichloro‐1‐Alkanols with Methylmagnesium Iodide

Kimpe¹,

Verhé²,

Buyck³

et al. 1979

Bulletin des Soc Chimique

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sium iodide in ether under reflux into highly sterically hindered alkohols. The mechanism proceeds by a pseudo pinacol type rearrangement of the initially formed carbonyl adduct. The mechanism of the rearrangement was proven by the synthesis of authentic reaction intermediates. The rearrangement was also extended to l-aryl-2,2-dichloro-l-alkanols which behaved analogously towards methylmagnesium iodide.l-Aryl-2,2-dichloro-l-alkanones were shown to rearrange with methyl magne-

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Kinetic studies and improved reaction conditions for the halogen shift rearrangments of aryldihalopropanols

Cited by 5 publications

References 11 publications

Cyclic Enolates of Ni and Pd: Equilibrium between C‐ and O‐Bound Tautomers and Reactivity Studies

Cyclic Enolates of Ni and Pd: Equilibrium between C‐ and O‐Bound Tautomers and Reactivity Studies

Synthesis and reactivity ofα-halogenated ketones

Rearrangement of 1‐aryl‐2,2‐Dichloro‐1‐Alkanones and 1‐Aryl‐2,2‐Dichloro‐1‐Alkanols with Methylmagnesium Iodide

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