Bamford-Stevens Reaction

Definition:

Formation of olefins by base-promoted decomposition of p-toluenesulfonylhydrazones of aldehydes and 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. W. R. Bamford, T. S. Stevens, J. Chem. Soc. 4735 (1952).

Recent academic references: Click here for more references

2. Facile entry to the tetracyclic 5-7-6-3 tigliane ring system

• Ovaska, T. V.; Reisman, S. E.; Flynn, M. A.; Org. Lett.; 3(1); 115-117 (2001).

3. Direct Conversion of Tosylhydrazones to tert-Butyl Ethers under Bamford-Stevens Reaction Conditions

• Chandrasekhar, S.; Rajaiah, G.; Chandraiah, L.; Swamy, D. Narsimha Synlett; 11, 2001

4. Structural and stereoelectronic requirements for the inhibition of mammilian 2,3-oxidosqualene cyclase by substituted isoquinoline derivatives. 

• Barth, M. M.; et al.; J. Med. Chem.; 39(12); 2302-2312 (1996).

5.   http://www.chm.bris.ac.uk/org/aggarwal/ylide3.pdf

Recent process references:

Mechanism: http://www.arkat.org/arkat/journal/Named Reactions/Bamford.htm

Scope and Limitations:

• Aprotic solvent systems are generally employed (higher yielding and faster) due to mechanistic considerations. Higher boiling ethers and sodium alkoxides are often used. ^B
• Reaction mechanism depends on solvent: ^{A, B}

  • Protic solvents give rise to a carbenium ion followed by loss of a proton (as above)
  • Aprotic solvents engender a carbene intermediate followed be a 1,2 hydride shift.

Synonyms:

Shapiro reaction: treatment of ketone derived p-toluenesulfonylhydrazones with alkyl lithium reagents