Studies on the Grignard Reaction‐VI. Steric Effects in the Grignard Addition Reaction on Ketones

Schoote, J. van; Anteunis, M.

doi:10.1002/bscb.19630721113

Bulletin des Soc Chimique

1963

DOI: 10.1002/bscb.19630721113

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Studies on the Grignard Reaction‐VI. Steric Effects in the Grignard Addition Reaction on Ketones

J. van Schoote

M. Anteunis

Abstract: The reactivity in the normal Grignard addition reaction is greatly reduced when the ketone is branched in the α‐position. Alkylation in β‐position has only slight effect and in the γ‐position there is no effect at all.

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Studies on the Grignard Reaction‐VII (¹) on the Mechanism of the Grignard Reagent Formation and the Wurtz Side Reaction in Ether

Anteunis

Schoote

1963

Bulletin des Soc Chimique

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In contradiction with accepted views about Wurtz coupling reactions during the preparation of Grignard solutions, the highly accurate Volhard titrimetric and the complexometric method show no difference. Checking the amount of coupling product by direct GLC the obtained results are discussed on the basis of a new mechanistic scheme, which assumes the formation of univalent magnesium radicals. These either disproportionate after preparation, or stay bonded as subhalide.

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Studies on the Grignard Reaction‐VII (¹) on the Mechanism of the Grignard Reagent Formation and the Wurtz Side Reaction in Ether

Anteunis

Schoote

1963

Bulletin des Soc Chimique

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Reactions of Et₃ZnLi with Ketones: Electronic and Steric Effects¹

Musser

Richey

2000

J. Org. Chem.

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Toluene solutions of composition Et(3)ZnLi react rapidly with aldehydes and ketones to form addition products. Et(3)ZnNa and Et(3)ZnK solutions react readily with the same substrates although metalation, as well as addition, is significant with substrates having alpha-hydrogens. The Et(3)ZnM solutions react with 2-cyclohexenone to give mainly the 1,4-addition product. Relative rates of addition of Et(3)ZnLi to substituted acetophenones give a Hammett rho of 2.78. Addition of Et(3)ZnLi to acetophenone is slowed significantly by alpha and ortho methyl substituents; relative rates of addition to acetophenone, o-methylacetophenone, and tert-butyl phenyl ketone are 1.00, 0.012, and 0.003.

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Studies on the Grignard Reaction‐VI. Steric Effects in the Grignard Addition Reaction on Ketones

Abstract: The reactivity in the normal Grignard addition reaction is greatly reduced when the ketone is branched in the α‐position. Alkylation in β‐position has only slight effect and in the γ‐position there is no effect at all.

Cited by 2 publications

References 1 publication

Studies on the Grignard Reaction‐VII (¹) on the Mechanism of the Grignard Reagent Formation and the Wurtz Side Reaction in Ether

Studies on the Grignard Reaction‐VII (¹) on the Mechanism of the Grignard Reagent Formation and the Wurtz Side Reaction in Ether

Reactions of Et₃ZnLi with Ketones: Electronic and Steric Effects¹

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Studies on the Grignard Reaction‐VI. Steric Effects in the Grignard Addition Reaction on Ketones

Abstract: The reactivity in the normal Grignard addition reaction is greatly reduced when the ketone is branched in the α‐position. Alkylation in β‐position has only slight effect and in the γ‐position there is no effect at all.

Cited by 2 publications

References 1 publication

Studies on the Grignard Reaction‐VII (1) on the Mechanism of the Grignard Reagent Formation and the Wurtz Side Reaction in Ether

Studies on the Grignard Reaction‐VII (1) on the Mechanism of the Grignard Reagent Formation and the Wurtz Side Reaction in Ether

Reactions of Et3ZnLi with Ketones: Electronic and Steric Effects1

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Product

Resources

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Studies on the Grignard Reaction‐VII (¹) on the Mechanism of the Grignard Reagent Formation and the Wurtz Side Reaction in Ether

Studies on the Grignard Reaction‐VII (¹) on the Mechanism of the Grignard Reagent Formation and the Wurtz Side Reaction in Ether

Reactions of Et₃ZnLi with Ketones: Electronic and Steric Effects¹