The Barbier - Grignard-type carbonyl alkylation using unactivated alkyl halides in water

Journal of the American Chemical Society

Volumn 125, Issue 14, 2003, Pages 4062-4063

  Keh, Charlene C K ^a   Wei, Chunmei ^a   Li, Chao Jun ^a  

^a Tulane University   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALDEHYDE DERIVATIVE; BROMINE; CARBONYL DERIVATIVE; CHLORIDE; COPPER; HALIDE; IODIDE; METAL COMPLEX; METHANOL; WATER; ZINC;

ALKYLATION; ARTICLE; CATALYSIS; CHEMICAL BOND; CHEMICAL STRUCTURE; DERIVATIZATION; PROTON NUCLEAR MAGNETIC RESONANCE; REACTION ANALYSIS; STRUCTURE ANALYSIS;

EID: 0037427242     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja029649p     Document Type: Article

References (38)

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32. Conjugated addition and imine additions have been reported before; however, unlike the aldehyde addition, the intermediates in these reactions are stabilized by the carbonyl or the aryl groups, respectively; for examples, see: Huang, T. S.; Keh, C. C. K.; Li, C. J. Chem. Commun. 2002, 2440. Miyabe, H.; Ueda, M.; Nishimura, A.; Naito, T. Org. Lett. 2002, 4, 131.
33. Conjugated addition and imine additions have been reported before; however, unlike the aldehyde addition, the intermediates in these reactions are stabilized by the carbonyl or the aryl groups, respectively; for examples, see: Huang, T. S.; Keh, C. C. K.; Li, C. J. Chem. Commun. 2002, 2440. Miyabe, H.; Ueda, M.; Nishimura, A.; Naito, T. Org. Lett. 2002, 4, 131.
34. Li, C. J. Acc. Chem. Res. 2002, 35, 533.
35. Further details are provided in the Supporting Information.
36. No reaction was observed with aliphatic aldehydes such as undecanal, 2,2-dimethylpropionaldehyde, cyclohexancarboxaldehyde. Ketones such as benzophenone, acetophenone, 2-hexanone, cyclohexanone, and cyclopentanone also did not result in the desired product along with unsaturated carbonyls such as 4-hexen-3-one and 2,2-dimethyl-4-pentenal.
37. 1H NMR showed an inseparable mix of reduced products. This was attributed to some reduction of the nitro group under the reaction conditions.
38. ,4-Dimethylbenzaldehyde and 2,4-bis(trifluoromethyl)benzaldehyde were compared in an analogous manner but had poor isolated yields of 17 and 8%, respectively, possibly due to steric effects.