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RMgX Grignard
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O M OR Ester enolate OH R O OR R
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O M R Ketone enolate OH O R R
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NR2 R Enamine OH NR2 R RO R RO O
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O M R
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RNH2 amine (primary amine) N R R R H R
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MCN Cyanide OH H CN
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ROH/ ROM alcohol/ alkoxide RO R OR H
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H2O/ MOH water/ hydroxide HO R OH H R
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NaBH4 Sodium borohydride OH H H R
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LiAlH4 Lithium aluminum hydride OH H H
OH H R R
Aldehyde
2 alcohol
Aldol Reaction
Aldol Reaction
heating under basic conditions will lead to elimination of OH - Aldol condensation also note that reaction can be reversible under basic conditions : Retro-aldol reaction O OH Cl R 3 alcohol R R R O O OR R O O R R O NR2 R
Knoevenagel Condensation
Imine (aldimine)
Cyanohydrin
Hydrate (usu. thermodynaically disfavored, except for electron poor aldehydes) If aldehyde is enolizable, hydroxide can form enolate. O
1 alcohol
1 alcohol
O RO O
OH R R R
O NHR R
O CN R
O OR R
OH OH H 2 alcohol R H R
OH H H 2 alcohol
Acyl chloride
keto ester
Acid nitrile
Ester
Carboxylic acid
O O R'
OH R R R 3 alcohol OH R
O OR R
O R R
NR2 R RO
O R CN R
O OR R
O OH Borderline R
OH H H
Anhydride O
R O OR R
Amide N R R R'
Ester RO R OR R'
1 alcohol OH R R' H
R'
R'
Ketone
3 alcohol
Aldol Reaction
Aldol Reaction
Note: best when ketones are identical or when only one can enolize (to avoid scrambling) O O R O OR R O O R R O NR2 R RO O OH R
Imine (ketimine)
Hydrate see above: even less favored than with aldehydes due to sterics O
2 alcohol
2 alcohol
O R RHN NC
O R RO
O R RO
Varies with conditions: 1,2 adduct is kinetic product, 1,4 adduct is thermodynamic.
Michael Reaction
Michael Reaction O R
Note: in both cases, very prone to the reverse reaction (elimination) O O NHR NR R OR'
OH OR R R R R
O OR R
O R Borderline Borderline R
Ester O
3 alcohol
Amide
Transesterification Saponification Can be done under basic (basic conditions) or acidic conditions. Can also hydrolyze with aqueous acid O R OR' NR
1 alcohol OH H H 1 alcohol R
Carboxylic acid
Usually requires dehydration agent (e.g. DCC) 1 and 2 amides: deprotonation 3amides: NR 1 and 2 amides: deprotonation 3amides: NR NR
Fischer esterification (requires acid, heat) Borderline reaction: requires strong acid, alcohol as solvent, heat O R OH NR
H R NH2 H Amine
NH2
Deprotonation
NR
NR
NR
Amide O O OR Enolate Alkylation R R R NR2 R RO R Alkyl halide Enolate Alkylation Stork enamine reaction note: capable of alkylating a second time Amine caution! product is a good nucleophile; can obtain multiple alkylations Williamson Ether Synthesis requires basic conditions O O R R NHR R CN R OR
Alkane