Henry Reaction

Definition:

Base-catalyzed aldol-type condensation, q.v., of nitroalkanes with aldehydes or ketones:

Frequency of appearance:

        This bar graph represents all of the online articles that were found to contain this specific name reaction in the title of the article. Tetrahedron letters, Tetrahedron, Synthetic letters, Synthesis, Journal of Organic Chemistry and Journal of the American Chemical Society are represented here. This table by no means represents the periodicity of the name reaction found in the literature.

Original reference:

1. Henry, L. Compt. Rend., 1895, 120, 1265.

Recent academic references: Click here for more references

2. Copper-Catalyzed Enantioselective Henry Reactions of -Keto Esters: An Easy Entry to Optically Active -Nitro-hydroxy Esters and -Amino--hydroxy Esters

• Christensen, C.; Juhl, K.; Hazell, R. G.; Jorgensen, K. A.; J. Org. Chem.; 2002; 67(14); 4875-4881.

3. A Dendritic Active Site: Catalysis of the Henry Reaction

• Davis, A. V.; Driffield, M.; Smith, D. K.; Org. Lett.; 2001; 3(20); 3075-3078.  

4. P(RNCH₂CH₂)₃N: An Efficient Promoter for the Nitroaldol (Henry) Reaction

• Kisanga, P. B.; Verkade, J. G.; J. Org. Chem.; 1999; 64(12); 4298-4303.  

5. Nitroaldol reaction in aqueous media: An important improvement of the Henry reaction

• Ballini, R.; Bosica, G.; J. Org. Chem.; 1997; 62(2); 425-427.  

6. http://cmds.kaist.ac.kr/%EB%85%BC%EB%AC%B8%EC%8B%A4%EC%A0%81/%EA%B9%80%EC%9A%A9%ED%95%B4/yh1.pdf

Recent process papers:

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Mechanism:

Scope and Limitations:

• Bases: hydroxides, carbonates, alkoxides, ammonium acetate, KF and amines.⁵
• Cannizaro may compete with aldehydes.⁵
• Aldol may compete with aldehydes having active alphe hydrogens.⁵
• Nitroalkanols may be isolated (basicity must be carefully watched).⁵

Synonyms:

• nitroaldol reaction