Chemistry of Carbonyl Compounds McM 1912

1
Chemistry of Carbonyl Compounds (McM 19-12)
Nucleophilic addition / substitution
May also be acid cat.
2
The Cannizzarro reaction (McM 19.13) Hydride as
leaving group!
3
Conjugate Addition (McM 19.14)
Michael acceptor

• 1,2-addition, Ex
• Alchohols
• Organolithium

• 1,4-addition, Ex
• Amines
• Organocuprates

Michael reaction (McM 23.11)
4
Robinson Annulation (McM 23.13)
Ring forming react. annulus (lat.) ring
5
E

• - Alkyl halides
• Carbonyl compounds (Aldol, Claissen condens.)
• - Halides

6
Michael acceptor
Enolizable
Alkylation of enolate anions (McM 22.8)
Base Strong, sterical hindrance
Ketones, esters, nitriles (Aldehydes
condensation)
7
Alkylation of 1,3-dicarbonyl compounds followed
by decarboxylation
8
Enamines as enolate equivalents (McM 23.12, Lab
ex. 11)
Synthesis of enamines (cf McM 19.9)
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Reactivity of enamines

• Alkylation (alkyl halides)
• Conjugate addition (Michael acceptors)
• Acylation (acid halides)

• Monoalkylation
• No strong base

10
Halogenation of enolate anions (McM 22.7)
11
Halogenation of neutral enols (McM 22.3)
mainly monohalogenated prod.
a-Bromination of acids (McM 22.4)
12
Carbonyl condensations in nature (McM 21.8, 23.14)
Acyl-CoA
Acetyl-CoA (Acetyl co-enzyme A)
Synthesis of Acetylcholine (neurotransmittor)
13
(No Transcript)
14
Polyesters, polyamides etc (McM 21.9)
Acyl subst react
Step-Growth polymers (Chain-Growth polymers
Polyenes)