1 Nucleophilic reactions involving enolate anions Aldehydes, Ketons and other carbonyl compounds...

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1 Nucleophilic reactions involving enolate anions Aldehydes, Ketons and other carbonyl compounds having H on α-C -> in equilibrium (in solution) -> Keto-Enol tautomerization

Transcript of 1 Nucleophilic reactions involving enolate anions Aldehydes, Ketons and other carbonyl compounds...

Page 1: 1 Nucleophilic reactions involving enolate anions Aldehydes, Ketons and other carbonyl compounds having H on α-C -> in equilibrium (in solution) -> Keto-Enol.

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Nucleophilic reactions involving enolate anions

Aldehydes, Ketons and other carbonyl compounds having H on α-C -> in equilibrium (in solution) -> Keto-Enol tautomerization

Page 2: 1 Nucleophilic reactions involving enolate anions Aldehydes, Ketons and other carbonyl compounds having H on α-C -> in equilibrium (in solution) -> Keto-Enol.

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Nucleophilic reactions involving enolate anions

Page 3: 1 Nucleophilic reactions involving enolate anions Aldehydes, Ketons and other carbonyl compounds having H on α-C -> in equilibrium (in solution) -> Keto-Enol.

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Nucleophilic reactions involving enolate anions

Page 4: 1 Nucleophilic reactions involving enolate anions Aldehydes, Ketons and other carbonyl compounds having H on α-C -> in equilibrium (in solution) -> Keto-Enol.

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Nucleophilic reactions involving enolate anions

Enolate anionConjugated base

Page 5: 1 Nucleophilic reactions involving enolate anions Aldehydes, Ketons and other carbonyl compounds having H on α-C -> in equilibrium (in solution) -> Keto-Enol.

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Nucleophilic reactions involving enolate anions

Hydrogen Exchange

Racemization

Page 6: 1 Nucleophilic reactions involving enolate anions Aldehydes, Ketons and other carbonyl compounds having H on α-C -> in equilibrium (in solution) -> Keto-Enol.

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Nucleophilic reactions involving enolate anions

Conjugation

Enol-Form -> Keto-Form

Progesterone(female sex hormone)

Page 7: 1 Nucleophilic reactions involving enolate anions Aldehydes, Ketons and other carbonyl compounds having H on α-C -> in equilibrium (in solution) -> Keto-Enol.

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Nucleophilic reactions involving enolate anions

Halogenation

Page 8: 1 Nucleophilic reactions involving enolate anions Aldehydes, Ketons and other carbonyl compounds having H on α-C -> in equilibrium (in solution) -> Keto-Enol.

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Nucleophilic reactions involving enolate anions

Alkylation of enolate anion

Enolate anion acting as carbanion nucleophiles in SN2 reaction

Page 9: 1 Nucleophilic reactions involving enolate anions Aldehydes, Ketons and other carbonyl compounds having H on α-C -> in equilibrium (in solution) -> Keto-Enol.

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Nucleophilic reactions involving enolate anions

Alkylation of enolate anion

Reaction not possible with aryl halides

Page 10: 1 Nucleophilic reactions involving enolate anions Aldehydes, Ketons and other carbonyl compounds having H on α-C -> in equilibrium (in solution) -> Keto-Enol.

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Nucleophilic reactions involving enolate anions

Alkylation of enolate anion

Page 11: 1 Nucleophilic reactions involving enolate anions Aldehydes, Ketons and other carbonyl compounds having H on α-C -> in equilibrium (in solution) -> Keto-Enol.

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Nucleophilic reactions involving enolate anions

Alkylation of enolate anion

Page 12: 1 Nucleophilic reactions involving enolate anions Aldehydes, Ketons and other carbonyl compounds having H on α-C -> in equilibrium (in solution) -> Keto-Enol.

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Nucleophilic reactions involving enolate anions

Addition-dehydration: Aldol reaction

Carbonyl compounds reacting as electrophiles -> aldol reaction

Aldehydes are better electrophiles than ketons-> aldol reaction more favourable with aldehydes

Page 13: 1 Nucleophilic reactions involving enolate anions Aldehydes, Ketons and other carbonyl compounds having H on α-C -> in equilibrium (in solution) -> Keto-Enol.

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Nucleophilic reactions involving enolate anions

Addition-dehydration: Aldol reaction

mixed aldol reaction

Page 14: 1 Nucleophilic reactions involving enolate anions Aldehydes, Ketons and other carbonyl compounds having H on α-C -> in equilibrium (in solution) -> Keto-Enol.

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Nucleophilic reactions involving enolate anions

Addition-dehydration: Aldol reaction

Product from aldol reaction dehydrates by heating in acid or base -> α,β unsaturated carbonyl compound

Under basic conditions -> E1cb (elimination-unimolecular-conjugated base)

Page 15: 1 Nucleophilic reactions involving enolate anions Aldehydes, Ketons and other carbonyl compounds having H on α-C -> in equilibrium (in solution) -> Keto-Enol.

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Nucleophilic reactions involving enolate anions

Addition-dehydration: Aldol reaction

Intramolecular aldol reaction

Page 16: 1 Nucleophilic reactions involving enolate anions Aldehydes, Ketons and other carbonyl compounds having H on α-C -> in equilibrium (in solution) -> Keto-Enol.

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Nucleophilic reactions involving enolate anions

Other stabilized anions as nucleophiles: nitriles and nitromethane

Page 17: 1 Nucleophilic reactions involving enolate anions Aldehydes, Ketons and other carbonyl compounds having H on α-C -> in equilibrium (in solution) -> Keto-Enol.

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Nucleophilic reactions involving enolate anions

Other stabilized anions as nucleophiles: nitriles and nitromethane

Page 18: 1 Nucleophilic reactions involving enolate anions Aldehydes, Ketons and other carbonyl compounds having H on α-C -> in equilibrium (in solution) -> Keto-Enol.

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Nucleophilic reactions involving enolate anions

Other stabilized anions as nucleophiles: nitriles and nitromethane

Page 19: 1 Nucleophilic reactions involving enolate anions Aldehydes, Ketons and other carbonyl compounds having H on α-C -> in equilibrium (in solution) -> Keto-Enol.

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Nucleophilic reactions involving enolate anions

Enamines as nucleophiles

Page 20: 1 Nucleophilic reactions involving enolate anions Aldehydes, Ketons and other carbonyl compounds having H on α-C -> in equilibrium (in solution) -> Keto-Enol.

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Nucleophilic reactions involving enolate anions

Enamines as nucleophiles

Page 21: 1 Nucleophilic reactions involving enolate anions Aldehydes, Ketons and other carbonyl compounds having H on α-C -> in equilibrium (in solution) -> Keto-Enol.

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Nucleophilic reactions involving enolate anions

Enamines as nucleophiles

Page 22: 1 Nucleophilic reactions involving enolate anions Aldehydes, Ketons and other carbonyl compounds having H on α-C -> in equilibrium (in solution) -> Keto-Enol.

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Nucleophilic reactions involving enolate anions

Enolate anions from carboxylic acid derivates

Page 23: 1 Nucleophilic reactions involving enolate anions Aldehydes, Ketons and other carbonyl compounds having H on α-C -> in equilibrium (in solution) -> Keto-Enol.

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Nucleophilic reactions involving enolate anions

Enolate anions from carboxylic acid derivates

base

More favourable with ketons and aldehydes

Page 24: 1 Nucleophilic reactions involving enolate anions Aldehydes, Ketons and other carbonyl compounds having H on α-C -> in equilibrium (in solution) -> Keto-Enol.

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Nucleophilic reactions involving enolate anions

Enolate anions from carboxylic acid derivates


Chapter 22 · Chapter 22 The Chemistry of Enolate Ions, Enols, and α,β ... • 22.11 Organic Synthesis with Conjugate‐Addion Reacons 2 ...

Chapter 22 · Chapter 22 The Chemistry of Enolate Ions, Enols, and α,β ... • 22.11 Organic Synthesis with Conjugate‐Addion Reacons 2 ...

Postpr int - DiVA portal431819/FULLTEXT01.pdf · Postpr int This is the accepted ... oxycarbonyl compounds is via oxidation of an enolate, ... amount of 4-iodotoluene was oxidized

Postpr int - DiVA portal431819/FULLTEXT01.pdf · Postpr int This is the accepted ... oxycarbonyl compounds is via oxidation of an enolate, ... amount of 4-iodotoluene was oxidized

Morpholine Ketene Aminal as Amide Enolate Surrogate in ......Morpholine Ketene Aminal as Amide Enolate Surrogate in Iridium-Catalyzed Asymmetric Allylic Alkylation Yeshua Sempere,

Morpholine Ketene Aminal as Amide Enolate Surrogate in ......Morpholine Ketene Aminal as Amide Enolate Surrogate in Iridium-Catalyzed Asymmetric Allylic Alkylation Yeshua Sempere,

Stereoselective reactions of enolatesgjrowlan/stereo2/lecture7.pdf · Addition of an electrophile to an enolate • Finally, need to know the trajectory of approach of the enolate

Stereoselective reactions of enolatesgjrowlan/stereo2/lecture7.pdf · Addition of an electrophile to an enolate • Finally, need to know the trajectory of approach of the enolate

CH 10. ALDEHYDES ET CETONES - lachimie.org · et des électrons σ fermement ... En partant des données enthalpiques des énergies de liaison, le calcul de la ... Cétone Enol ΔG°

CH 10. ALDEHYDES ET CETONES - lachimie.org · et des électrons σ fermement ... En partant des données enthalpiques des énergies de liaison, le calcul de la ... Cétone Enol ΔG°

Organic Chemistry II / CHEM 252 Chapter 17 – Aldehydes …alpha.chem.umb.edu/.../Lecture_Chapter_17.pdf · Organic Chemistry II / CHEM 252 Chapter 17 ... 8 Reactions via Enols/Enolate

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CH. 17 - ENOLS AND ENOLATE ANIONS: ALKYLATION AND CONDENSATIONlightcat-files.s3.amazonaws.com/packets/admin_organic-2-organic... · Once an aldol condensation is completed, an electrophilic

CH. 17 - ENOLS AND ENOLATE ANIONS: ALKYLATION AND CONDENSATIONlightcat-files.s3.amazonaws.com/packets/admin_organic-2-organic... · Once an aldol condensation is completed, an electrophilic

SUPPLEMENTAL INFORMATION – Lab Documentation …chemh215/CHEM216/Experiment2/jce2004p1488w_ci… · enolate anion derived from a 1,3 ... formed via ready dehydration of the intermediate

SUPPLEMENTAL INFORMATION – Lab Documentation …chemh215/CHEM216/Experiment2/jce2004p1488w_ci… · enolate anion derived from a 1,3 ... formed via ready dehydration of the intermediate

O H OH H C CH ceto enol - campus.usal.escampus.usal.es/~gqft/documents/tema21.pdf · La aplicación más importante de los enolatos de ácidos carboxílicos consiste en el ataque

O H OH H C CH ceto enol - campus.usal.escampus.usal.es/~gqft/documents/tema21.pdf · La aplicación más importante de los enolatos de ácidos carboxílicos consiste en el ataque

CHAPTER 12 MECHANISM OF REACTION - SRM · PDF fileMECHANISM OF REACTION ALDOL CONDENSATION: An ... form, it involves the nucleophilic addition of a ketone enolate to an ... MICHAEL

CHAPTER 12 MECHANISM OF REACTION - SRM · PDF fileMECHANISM OF REACTION ALDOL CONDENSATION: An ... form, it involves the nucleophilic addition of a ketone enolate to an ... MICHAEL

III Enolate Chemistry - stuba.skszolcsanyi/education/files/Organicka chemia II... · III Enolate Chemistry Objectives By the end of this section you will: 1) know how to use the enol

III Enolate Chemistry - stuba.skszolcsanyi/education/files/Organicka chemia II... · III Enolate Chemistry Objectives By the end of this section you will: 1) know how to use the enol

Asymmetric Epoxidation of Enol Ethers and Esters Using ......and Technology Dr. Badr Alharbi. I would like to give thanks to my best friends Dr. Mouslim Messali and Dr. Ateyat allah

Asymmetric Epoxidation of Enol Ethers and Esters Using ......and Technology Dr. Badr Alharbi. I would like to give thanks to my best friends Dr. Mouslim Messali and Dr. Ateyat allah

Synthesis of Novel -Keto-Enol Derivatives Tethered ...

Synthesis of Novel -Keto-Enol Derivatives Tethered ...

Enolates, Enols, and Enamines Part 1 - Chemistry2011.org · Enolate Enol alkene + alcohol Enamine alkene + amine O ... Enolates, Enols, and Enamines Part 1 Lecture Supplement -- Page

Enolates, Enols, and Enamines Part 1 - Chemistry2011.org · Enolate Enol alkene + alcohol Enamine alkene + amine O ... Enolates, Enols, and Enamines Part 1 Lecture Supplement -- Page

Enols and Enolates - w3.ualg.ptw3.ualg.pt/~abrigas/qoii0708a11.pdf · enols and enolates are potential nucleophiles • Ketone enol • Ketone enolate ... Alkylation of Enolates Mechanism

Enols and Enolates - w3.ualg.ptw3.ualg.pt/~abrigas/qoii0708a11.pdf · enols and enolates are potential nucleophiles • Ketone enol • Ketone enolate ... Alkylation of Enolates Mechanism

Substitution αto a carbonyl center: Enol and enolate chemistry · Rate = first order in [CO] and zero order in [X 2] large primary KIE (6.1 for Br 2 of methyl cyclohexyl ketone in

Substitution αto a carbonyl center: Enol and enolate chemistry · Rate = first order in [CO] and zero order in [X 2] large primary KIE (6.1 for Br 2 of methyl cyclohexyl ketone in

1 Nucleophilic reactions involving enolate anions (2) Aldehydes, Ketons and other carbonyl compounds having H on α-C -> in equilibrium (in solution) ->

1 Nucleophilic reactions involving enolate anions (2) Aldehydes, Ketons and other carbonyl compounds having H on α-C -> in equilibrium (in solution) ->

B.Sc. Chemistry: Semester - I Basic Chemistry - I Paper No ... · Semi micro qualitative analysis of inorganic salt mixtures containing: Anions: (including interfering radical) Acetate,

B.Sc. Chemistry: Semester - I Basic Chemistry - I Paper No ... · Semi micro qualitative analysis of inorganic salt mixtures containing: Anions: (including interfering radical) Acetate,

α-Dicarbonylmonohydrazone und ihre Acylderivate als ... · PDF filesonanz tritt; die entsprechenden Signale f¨ur die Me- ... ein Methylen-Iminium-Kation und eine Enol-Azo-Verbindung,

α-Dicarbonylmonohydrazone und ihre Acylderivate als ... · PDF filesonanz tritt; die entsprechenden Signale f¨ur die Me- ... ein Methylen-Iminium-Kation und eine Enol-Azo-Verbindung,

Chapter 6 Formation of Carbon-Carbon σBonds via Enolate ...pnorris.people.ysu.edu/Semesters/6942S2008/Chapter6.pdf6.2 – Direct Alkylation of Simple Enolates – Ester Enolates –

Chapter 6 Formation of Carbon-Carbon σBonds via Enolate ...pnorris.people.ysu.edu/Semesters/6942S2008/Chapter6.pdf6.2 – Direct Alkylation of Simple Enolates – Ester Enolates –