Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of...
Transcript of Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of...
![Page 1: Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones](https://reader035.fdocuments.net/reader035/viewer/2022071415/610f5d7f46e8a36075490d49/html5/thumbnails/1.jpg)
Chapter 16. Aldehydes and
Ketones: Nucleophilic
Addition Reactions
Based on McMurry’s Organic Chemistry, 7th edition
![Page 2: Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones](https://reader035.fdocuments.net/reader035/viewer/2022071415/610f5d7f46e8a36075490d49/html5/thumbnails/2.jpg)
2
Aldehydes and Ketones
Aldehydes (RCHO) and ketones (R2CO) are
characterized by the the carbonyl functional group
(C=O)
The compounds occur widely in nature as
intermediates in metabolism and biosynthesis
![Page 3: Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones](https://reader035.fdocuments.net/reader035/viewer/2022071415/610f5d7f46e8a36075490d49/html5/thumbnails/3.jpg)
3
Why this Chapter?
Much of organic chemistry involves the
chemistry of carbonyl compounds
Aldehydes/ketones are intermediates in
synthesis of pharmaceutical agents,
biological pathways, numerous industrial
processes
An understanding of their properties is
essential
![Page 4: Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones](https://reader035.fdocuments.net/reader035/viewer/2022071415/610f5d7f46e8a36075490d49/html5/thumbnails/4.jpg)
4
19.1 Naming Aldehydes and
Ketones
Aldehydes are named by replacing the terminal -e of the corresponding alkane name with –al
The parent chain must contain the CHO group
The CHO carbon is numbered as C1
If the CHO group is attached to a ring, use the suffix carbaldehyde.
See Table 19.1 for common names
![Page 5: Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones](https://reader035.fdocuments.net/reader035/viewer/2022071415/610f5d7f46e8a36075490d49/html5/thumbnails/5.jpg)
5
Naming Ketones
Replace the terminal -e of the alkane name with –one
Parent chain is the longest one that contains the
ketone group
Numbering begins at the end nearer the carbonyl
carbon
![Page 6: Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones](https://reader035.fdocuments.net/reader035/viewer/2022071415/610f5d7f46e8a36075490d49/html5/thumbnails/6.jpg)
6
Ketones with Common Names
IUPAC retains well-used but unsystematic names for
a few ketones
![Page 7: Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones](https://reader035.fdocuments.net/reader035/viewer/2022071415/610f5d7f46e8a36075490d49/html5/thumbnails/7.jpg)
7
Ketones and Aldehydes as
Substituents
The R–C=O as a substituent is an acyl group, used with the suffix -yl from the root of the carboxylic acid CH3CO: acetyl; CHO: formyl; C6H5CO: benzoyl
The prefix oxo- is used if other functional groups are present and the doubly bonded oxygen is labeled as a substituent on a parent chain
![Page 8: Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones](https://reader035.fdocuments.net/reader035/viewer/2022071415/610f5d7f46e8a36075490d49/html5/thumbnails/8.jpg)
8
19.2 Preparation of Aldehydes and
Ketones Preparing Aldehydes
Oxidize primary alcohols using pyridinium chlorochromate
Alkenes with a vinylic hydrogen can undergo oxidative cleavage when treated with ozone, yielding aldehydes
Reduce an ester with diisobutylaluminum hydride (DIBAH)
![Page 9: Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones](https://reader035.fdocuments.net/reader035/viewer/2022071415/610f5d7f46e8a36075490d49/html5/thumbnails/9.jpg)
9
Preparing Ketones
Oxidize a 2° alcohol
Many reagents possible: choose for the specific
situation (scale, cost, and acid/base sensitivity)
![Page 10: Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones](https://reader035.fdocuments.net/reader035/viewer/2022071415/610f5d7f46e8a36075490d49/html5/thumbnails/10.jpg)
10
Ketones from Ozonolysis
Ozonolysis of alkenes yields ketones if one of the unsaturated carbon atoms is disubstituted
![Page 11: Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones](https://reader035.fdocuments.net/reader035/viewer/2022071415/610f5d7f46e8a36075490d49/html5/thumbnails/11.jpg)
11
Aryl Ketones by Acylation
Friedel–Crafts acylation of an aromatic ring with an
acid chloride in the presence of AlCl3 catalyst
![Page 12: Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones](https://reader035.fdocuments.net/reader035/viewer/2022071415/610f5d7f46e8a36075490d49/html5/thumbnails/12.jpg)
12
Methyl Ketones by Hydrating Alkynes
Hydration of terminal alkynes in the presence of Hg2+
(catalyst: Section 8.4)
![Page 13: Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones](https://reader035.fdocuments.net/reader035/viewer/2022071415/610f5d7f46e8a36075490d49/html5/thumbnails/13.jpg)
13
19.3 Oxidation of Aldehydes and
Ketones CrO3 in aqueous acid oxidizes aldehydes to carboxylic acids
efficiently at room temperature in good yield
Silver oxide, Ag2O, in aqueous ammonia (Tollens’ reagent)
oxidizes aldehydes without harming carbon-carbon double bond
or other acidic- sensitive functional groups in a molecule
![Page 14: Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones](https://reader035.fdocuments.net/reader035/viewer/2022071415/610f5d7f46e8a36075490d49/html5/thumbnails/14.jpg)
14
Hydration of Aldehydes
Aldehyde oxidations occur through 1,1-diols (“hydrates”)
Reversible addition of water to the carbonyl group
Aldehyde hydrate is oxidized to a carboxylic acid by usual reagents for alcohols
![Page 15: Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones](https://reader035.fdocuments.net/reader035/viewer/2022071415/610f5d7f46e8a36075490d49/html5/thumbnails/15.jpg)
15
Ketones Oxidize with Difficulty
Undergo slow cleavage with hot, alkaline KMnO4
C–C bond next to C=O is broken to give carboxylic
acids
Reaction is practical for cleaving symmetrical ketones
Product mixtures are formed from unsymmetrical
ketones.
![Page 16: Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones](https://reader035.fdocuments.net/reader035/viewer/2022071415/610f5d7f46e8a36075490d49/html5/thumbnails/16.jpg)
16
19.4 Nucleophilic Addition Reactions of
Aldehydes and Ketones
Nu- approaches 75° to the plane of C=O and adds to C
A tetrahedral alkoxide ion intermediate is produced
![Page 17: Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones](https://reader035.fdocuments.net/reader035/viewer/2022071415/610f5d7f46e8a36075490d49/html5/thumbnails/17.jpg)
17
Nucleophiles
Nucleophiles can be negatively charged ( : Nu) or neutral ( : Nu) at the reaction site
The overall charge on the nucleophilic species is not considered
![Page 18: Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones](https://reader035.fdocuments.net/reader035/viewer/2022071415/610f5d7f46e8a36075490d49/html5/thumbnails/18.jpg)
Nucleophilic Addition Reactions of
Aldehydes and Ketones
18
The general reaction pathways of Nucleophilic Addition
Reactions of
Aldehydes and Ketones ,leads to an alcohol product or
the product with a
C= Nu bund.
![Page 19: Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones](https://reader035.fdocuments.net/reader035/viewer/2022071415/610f5d7f46e8a36075490d49/html5/thumbnails/19.jpg)
19
Relative Reactivity of Aldehydes
and Ketones Aldehydes are generally more reactive than ketones in
nucleophilic addition reactions
The transition state for addition is less congested and lower in energy for an aldehyde (a) than for a ketone (b)
Aldehydes have one large substituent bonded to the C=O: ketones have two
Electronically, aldehydes are more reactive than ketones because of the greater polarization of aldehyde carbonyl groups.
![Page 20: Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones](https://reader035.fdocuments.net/reader035/viewer/2022071415/610f5d7f46e8a36075490d49/html5/thumbnails/20.jpg)
20
Electrophilicity of Aldehydes and
Ketones Aldehyde C=O is more polarized than ketone C=O
As in carbocations, more alkyl groups stabilize + character
Ketone has more alkyl groups, stabilizing the C=O carbon inductively
![Page 21: Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones](https://reader035.fdocuments.net/reader035/viewer/2022071415/610f5d7f46e8a36075490d49/html5/thumbnails/21.jpg)
21
Reactivity of Aromatic Aldehydes
Aromatic aldehydes Less reactive in nucleophilic addition reactions than aliphatic aldehydes
Electron-donating resonance effect of aromatic ring makes C=O less reactive electrophile than the carbonyl group of an aliphatic aldehyde
![Page 22: Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones](https://reader035.fdocuments.net/reader035/viewer/2022071415/610f5d7f46e8a36075490d49/html5/thumbnails/22.jpg)
22
19.5 Nucleophilic Addition of H2O:
Hydration
Aldehydes and ketones react with water to yield 1,1-diols
Hyrdation is reversible: a diol can eliminate water
![Page 23: Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones](https://reader035.fdocuments.net/reader035/viewer/2022071415/610f5d7f46e8a36075490d49/html5/thumbnails/23.jpg)
23
Base-Catalyzed Addition of
Water Addition of water is catalyzed by both acid and base
The base-catalyzed hydration nucleophile is the
hydroxide ion, which is a much stronger nucleophile
than water
![Page 24: Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones](https://reader035.fdocuments.net/reader035/viewer/2022071415/610f5d7f46e8a36075490d49/html5/thumbnails/24.jpg)
24
Acid-Catalyzed Addition of Water
Protonation of C=O makes it
more electrophilic
![Page 25: Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones](https://reader035.fdocuments.net/reader035/viewer/2022071415/610f5d7f46e8a36075490d49/html5/thumbnails/25.jpg)
25
Addition of H-Y to C=O
Reaction of C=O with H-Y, where Y is
electronegative, gives an addition product (“adduct”)
Formation is readily reversible and does not normally
lead to a stable alcohol addition product.
![Page 26: Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones](https://reader035.fdocuments.net/reader035/viewer/2022071415/610f5d7f46e8a36075490d49/html5/thumbnails/26.jpg)
26
19.6 Nucleophilic Addition of HCN:
Cyanohydrin Formation Aldehydes and unhindered ketones react with HCN to yield
cyanohydrins, RCH(OH)CN
Addition of HCN is reversible and base-catalyzed, generating nucleophilic cyanide ion, CN- as KCN
Addition of CN to C=O yields a tetrahedral intermediate, which is then protonated
Equilibrium favors adduct
![Page 27: Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones](https://reader035.fdocuments.net/reader035/viewer/2022071415/610f5d7f46e8a36075490d49/html5/thumbnails/27.jpg)
27
Uses of Cyanohydrins
The nitrile group (CN) can be reduced with LiAlH4
to yield a primary amine (RCH2NH2)
Can be hydrolyzed by hot acid to yield a carboxylic
acid
![Page 28: Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones](https://reader035.fdocuments.net/reader035/viewer/2022071415/610f5d7f46e8a36075490d49/html5/thumbnails/28.jpg)
28
19.7 Nucleophilic Addition of Grignard
Reagents and Hydride Reagents: Alcohol
Formation
Treatment of aldehydes or ketones with Grignard
reagents yields an alcohol
Nucleophilic addition of the equivalent of a carbonanion, or carbanion. A carbon–magnesium bond is
strongly polarized, so a Grignard reagent reacts for all
practical purposes as R : MgX +.
![Page 29: Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones](https://reader035.fdocuments.net/reader035/viewer/2022071415/610f5d7f46e8a36075490d49/html5/thumbnails/29.jpg)
29
Mechanism of Addition of Grignard
Reagents
Complexation of C=O by Mg2+, Nucleophilic addition of R : ,protonation by dilute acid yields the neutral alcohol
Grignard additions are irreversible because a carbanion is not a leaving group
![Page 30: Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones](https://reader035.fdocuments.net/reader035/viewer/2022071415/610f5d7f46e8a36075490d49/html5/thumbnails/30.jpg)
30
Hydride Addition
Convert C=O to CH-OH
LiAlH4 and NaBH4 react as donors of hydride ion
Protonation after addition yields the alcohol
![Page 31: Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones](https://reader035.fdocuments.net/reader035/viewer/2022071415/610f5d7f46e8a36075490d49/html5/thumbnails/31.jpg)
31
19.8 Nucleophilic Addition of Amines:
Imine and Enamine Formation
RNH2 adds to C=O to form imines, R2C=NR (after loss of HOH)
R2NH yields enamines, R2NCR=CR2 (after loss of HOH)
(ene + amine = unsaturated amine)
![Page 32: Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones](https://reader035.fdocuments.net/reader035/viewer/2022071415/610f5d7f46e8a36075490d49/html5/thumbnails/32.jpg)
32
Imine Derivatives
Addition of amines with an atom containing a lone pair of electrons on the adjacent atom occurs very readily, giving useful, stable imines
For example, hydroxylamine forms oximes and 2,4-dinitrophenylhydrazine readily forms 2,4-dinitrophenylhydrazones These are usually solids and help in characterizing
liquid ketones or aldehydes by melting points
![Page 33: Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones](https://reader035.fdocuments.net/reader035/viewer/2022071415/610f5d7f46e8a36075490d49/html5/thumbnails/33.jpg)
33
![Page 34: Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones](https://reader035.fdocuments.net/reader035/viewer/2022071415/610f5d7f46e8a36075490d49/html5/thumbnails/34.jpg)
34
19.9 Nucleophilic Addition of Hydrazine: The
Wolff–Kishner Reaction
Treatment of an aldehyde or ketone with hydrazine, H2NNH2 and KOH converts the compound to an alkane
Originally carried out at high temperatures but with dimethyl sulfoxide as solvent takes place near room temperature
![Page 35: Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones](https://reader035.fdocuments.net/reader035/viewer/2022071415/610f5d7f46e8a36075490d49/html5/thumbnails/35.jpg)
35
19.10 Nucleophilic Addition of
Alcohols: Acetal Formation
Alcohols are weak nucleophiles but acid promotes
addition forming the conjugate acid of C=O
Addition yields a hydroxy ether, called a hemiacetal
(reversible); further reaction can occur
![Page 36: Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones](https://reader035.fdocuments.net/reader035/viewer/2022071415/610f5d7f46e8a36075490d49/html5/thumbnails/36.jpg)
36
Uses of Acetals
Reduce only the ester group of ethyl 4-oxopentanoate,
If Treatment of the starting keto ester with LiALH4 would
reduce both the keto and the ester groups to give a diol
product.
![Page 37: Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones](https://reader035.fdocuments.net/reader035/viewer/2022071415/610f5d7f46e8a36075490d49/html5/thumbnails/37.jpg)
37
For that ,the first converting the keto group to an acetal, then
reducing the ester with LiAlH4,and then removing the acetal
by treatment with aqueous acid.
![Page 38: Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones](https://reader035.fdocuments.net/reader035/viewer/2022071415/610f5d7f46e8a36075490d49/html5/thumbnails/38.jpg)
38
19.11 Nucleophilic Addition of Phosphorus
Ylides: The Wittig Reaction
The sequence converts C=O is to C=C
A phosphorus ylide adds to an aldehyde or ketone to yield a dipolar intermediate called a betaine
The intermediate spontaneously decomposes through a four-membered ring to yield alkene and triphenylphosphine oxide, (Ph)3P=O
Formation of the ylide is shown below
![Page 39: Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones](https://reader035.fdocuments.net/reader035/viewer/2022071415/610f5d7f46e8a36075490d49/html5/thumbnails/39.jpg)
The mechanism of Witting reaction
39
Aldehydes and ketones are
Converted into alkene
By this reaction.
![Page 40: Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones](https://reader035.fdocuments.net/reader035/viewer/2022071415/610f5d7f46e8a36075490d49/html5/thumbnails/40.jpg)
40
Uses of the Wittig Reaction
Can be used for monosubstituted, disubstituted, and trisubstituted alkenes but not tetrasubstituted alkenes The reaction yields a pure alkene of defined structure with methylenetriphenylphosphorane
For comparison, addition of CH3MgBr to cyclohexanone and dehydration with, yields a mixture of two alkenes
![Page 41: Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones](https://reader035.fdocuments.net/reader035/viewer/2022071415/610f5d7f46e8a36075490d49/html5/thumbnails/41.jpg)
41
19.13 Conjugate Nucleophilic Addition to
-Unsaturated Aldehydes and Ketones
A nucleophile can add to the C=C double bond of an ,-unsaturated aldehyde or ketone .
The initial product is a resonance-stabilized enolate ion, which is then protonated
![Page 42: Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones](https://reader035.fdocuments.net/reader035/viewer/2022071415/610f5d7f46e8a36075490d49/html5/thumbnails/42.jpg)
42
Conjugate Addition of Amines
Primary and secondary amines add to , -unsaturated aldehydes and ketones to yield -amino aldehydes and ketones
![Page 43: Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones](https://reader035.fdocuments.net/reader035/viewer/2022071415/610f5d7f46e8a36075490d49/html5/thumbnails/43.jpg)
Conjugate Addition of Alkyl Groups:
Organocopper Reactions
Conjugate addition of an alkyl group to an , -
unsaturated ketone (but not aldehyde) is more
useful by Grignard regent
Or addition of an alkyl
to an , -unsaturated ketone
Group is by Gilman reagent
(1 equivalent of cuprous
iodide and 2 equvalents of
organolithium)
43
![Page 44: Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones](https://reader035.fdocuments.net/reader035/viewer/2022071415/610f5d7f46e8a36075490d49/html5/thumbnails/44.jpg)
44
Conjugate Addition of Alkyl Groups: Organocopper Reactions
1, 2, 3 alkyl, aryl and alkenyl groups react but not alkynyl groups
![Page 45: Chapter 16. Aldehydes and Ketones: Nucleophilic Addition ... Chapter...3 Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones](https://reader035.fdocuments.net/reader035/viewer/2022071415/610f5d7f46e8a36075490d49/html5/thumbnails/45.jpg)
45
Mechanism of Alkyl Conjugate Addition
Conjugate nucleophilic addition of a diorganocopper anion, R2Cu, to an enone
Transfer of an R group and elimination of a neutral organocopper species, RCu