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NUCLEOPHILIC
ADDITIONS TO THE CARBONYL GROUP
OBJECTIVES
1. Describe the reactivity of carbonyl group towards the nucleophilic
addition (PAGE : 741)
2. Predict the products of cyanohydrin from synthesis of -hydroxy acids
and hydrolysis of nitriles (PAGE : 755)
3. Predict the products from the addition of Organometallic Reagents
Grignard and alkyl lithium reagents) to aldehydes and ketones. (PAGE
: 566-568, 776)
4. Predict the products from the addition of water (hydration) to aldehydes
and ketones (PAGE : 746)
5.. Predict the products of acetals and hemiacetal from the addition of
Alcohols and describe the formation of cyclic acetals (PAGE : 748) and
its uses as protecting group. (PAGE : 749)
6. Predict the products from the addition of amines to aldehydes and
ketones which produce Imines from 1o Amines (PAGE : 751), Enamines
from 2o Amines (PAGE : 754), Enamines for Alkylation of Ketones
(PAGE : 755)
7. Predict the products from Wittig Reaction (PAGE : 757-760)
Chapter 16
Groups
o Addition of a nucleophile to a carbonyl carbon occurs because
of the d+ charge at the carbon
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aminoalcohol
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it more electrophilic
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Acetals
Hemiacetals
An aldehyde or ketone dissolved in an alcohol will form an
equilibrium mixture containing the corresponding hemiacetal
A hemiacetal has a hydroxyl and alkoxyl group on the same carbon
Acylic hemiacetals are generally not stable, however, cyclic five- and six-
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Acetals
An aldehyde (or ketone) in the presence of excess alcohol and an
acid catalyst will form an acetal
H Formation of the acetal proceeds via the corresponding hemiacetal
H An acetal has two alkoxyl groups bonded to the same carbon
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favorable
H Such cyclic acetals are often used as protecting groups for aldehydes and
ketones
H These protecting groups can be removed using dilute aqueous acid
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Imines
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Enamines
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the ylide
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Addition of the ylide to the carbonyl leads to formation of a fourmembered ring oxaphosphetane
The oxaphophetane rearranges to the alkene and triphenylphosphine oxide
The driving force for the last reaction is formation of the very strong
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