The document discusses various carbonyl condensation reactions including aldol condensation, Claisen condensation, Knoevenagel condensation, and the Robinson Annulation. Aldol condensation involves the reaction of two carbonyl compounds where one has an α-hydrogen, resulting in a β-hydroxy aldehyde or ketone. The Claisen condensation involves the condensation of esters with α-hydrogens in the presence of base to form β-keto esters. The Robinson Annulation is a ring-forming reaction that uses a Michael reaction followed by an intramolecular aldol addition to form a cyclic compound.
The document discusses various carbonyl condensation reactions including aldol condensation, Claisen condensation, Knoevenagel condensation, and the Robinson Annulation. Aldol condensation involves the reaction of two carbonyl compounds where one has an α-hydrogen, resulting in a β-hydroxy aldehyde or ketone. The Claisen condensation involves the condensation of esters with α-hydrogens in the presence of base to form β-keto esters. The Robinson Annulation is a ring-forming reaction that uses a Michael reaction followed by an intramolecular aldol addition to form a cyclic compound.
The document discusses various carbonyl condensation reactions including aldol condensation, Claisen condensation, Knoevenagel condensation, and the Robinson Annulation. Aldol condensation involves the reaction of two carbonyl compounds where one has an α-hydrogen, resulting in a β-hydroxy aldehyde or ketone. The Claisen condensation involves the condensation of esters with α-hydrogens in the presence of base to form β-keto esters. The Robinson Annulation is a ring-forming reaction that uses a Michael reaction followed by an intramolecular aldol addition to form a cyclic compound.
How would you prepare the following compound by an enamine
synthesis?
Alkylation of the -carbon: (sd-62)
THE MICHAEL REACTION Addition of enolate ion to the -carbon of , -unsaturated carbonyl compound Michael Reaction.
75
76
77
78
Stork Enamine Reaction (Sd-64)
When an enamine is used as a nucleophile in place of an enolate in a Michael reaction, the reaction is called Stork Enamine Reaction.
ALDOL CONDENSATION: (sd-65)
A reaction between two molecules of RCHO/RCOR with hydrogen in basic condition -hydroxy aldehyde or -hydroxy ketone.
79
Dehydration of Aldol addition product (sd-66)
80
Dehydration sometimes occurs under the conditions in which the
aldol addition is carried out (without additional heating)(sd-67).
81
Crossed Aldol Condensations: (sd-68)
Condensation between two carbonyl compounds (only one of the carbonyl compounds has -hydrogen)
82
Intramolecular Aldol reactions: Certain dicarbonyl compounds
when treated with base undergo intramolecular aldol reactionscyclic products (5/6-membered).
MECHANISM:
83
Synthesis using aldol condensations (sd-70)
Aldol condensation 1. -hydroxy aldehyde or ketone 2. --unsaturated aldehyde/ketone Therefore look for these two functional groups and decide which aldehydes/ketones must be used for the starting materials.
Knoevenagel condensation (sd-71)
84
85
The Claisen condensation: (73)
Condensation involving molecules of an ester (with -H) in the presence of base a -keto ester.
86
Crossed Claisen condensation: ( sd-74)
Condensation between two different esters; Best results (to avoid mixtures) are obtained if only one of the esters has -H) Condensation between ketones and esters (either contain -H or not)
87
Both having H- :(sd-74a)
88
89
90
91
92
93
94
The Robinson Annulation (sd-79)
A ring forming reaction that involves: i) ii)
A Michael Reaction- to form a 1,5-diketone
1,5-diketone undergoes an intramolecular aldol addition cyclic compound