Sunday 21 February 2016

Organic Chemistry: C-C Bond Forming Reactions, Part III


8.   Reformatsky Reaction
This reactions is the condensation of a-halo esters with aldehydes or ketones in the presence of zinc to yield b-hydroxy esters.

The reaction involves the formation of a zinc enolate which is quite similar to Grignard reagent attacking nucleophilically on the aldehyde.






9.   Simmons-Smith Reactions

Simmons-Smith reaction is a stereospecific reaction of alkene with an organozinc carbenoid to form cyclopropane rings. The reaction involves the insertion of a methylene group.







10.                     Riemer-Tiemann Reaction

The ortho formylation of phenol is known as the Riemer-Tiemann reaction. The reaction involves a carbene intermediate produced from chloroform in the presence of NaOH, which then forms a C-C at the ortho position of the phenol.



11.                     Acyloin condensation

The reductive coupling of esters in the presence of sodium metal gives an a-hydroxy ketone. The reaction is known as acyloin condensation.








12.                     Arndt-Eistert Reaction

Arndt-Eistert reaction is the one carbon homologation of carboxylic acids. The reaction involves three stepes. I. conversion of carboxylic acid to acid chloride with thionyl chloride, II. Conversion of acid chloride to diazoketone with diazomethane, and III. Conversion of diazoketone to carboxylic acid which is one carbon higher than the starting material.


13. Gattermann Reaction

Formylation of aromatic rings by using HCN is the Gattermann reaction. A Lewis acid is used a catalyst leading to the formation of a C-C bond.



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