List of Reactions for KEM030/KEM031/LGKE61

p. 265

2 KOH

Other strong bases like NaOH can be used as well. Terminal alkynes can also be formed this way, but require 3 equivalents of the base.

dihalide alkyne

lecture 2

p. 266

xs HX

AcOH

Both halide ions bind to the same carbon atom, forming a geminal dihalide. Addition follows Markovnikov's rule for both steps.

alkyne dihalide

lecture 2

p. 266

xs X₂

CH₂Cl₂

This reaction proceeds via an alkenyl diahalide intermediate.

alkyne tetrahalide

lecture 2

p. 268

H₂O, H₂SO₄

HgSO₄

Mercury(Ⅱ)-catalyzed hydration of alkynes. Non-terminal alkenes can also be used, but this leads to a mixture of product due to two carbocation intermediates being equally substituted.

alkyne ketone

lecture 2

p. 270

1) BH₃ · THF

2) H₂O₂, H₂O, NaOH

Hydroboration-oxidation of alkynes. This reaction yields aldehydes with terminal alkynes. Non-terminal alkynes can also be used to yield ketones, but may lead to a mixture of products unless there's symmetry.

alkyne aldehyde

alkyne ketone

lecture 2

p. 272

H₂

Lindlar catalyst

This is a partial reduction that yields cis alkenes through syn addition. If a trans alkene is desired, Li/NH₃ should be used instead.

alkyne alkene

lecture 2

p. 272

H₂

Pd/C catalyst

This is a full reduction that breaks all π bonds of the alkyne. This reaction is not strong enough to reduce aromatic compounds like arenes.

alkyne alkane

lecture 2

H₂

Pd/C catalyst

alkene alkane

lecture 2

p. 275

NaNH₂

Deprotonating a terminal alkyne requires a strong base with a conjugate acid of pK_a > 25.

alkyne acetylide anion

lecture 2

p. 277

R'X

Acetylide anions can react with alkyl halides to form alkynes, forming a C−C bond in the process. To form terminal alkynes using this method, alkylate acetylene.

acetylide anion alkyne

alkyl halide alkyne

lecture 2

C−C forming

p. 292

HX

This addition reaction follows Markovnikov's rule.

alkene alkyl halide

lecture 2

p. 292

X₂

The resulting addition reaction in this case is anti. A compound that has halogens on adjacent carbons is called a vicinal dihalide

alkene dihalide

lecture 2

p. 297

HX

This reaction occurs via an S_N1 pathway. Non-tertiary alcohols can be used as well, but favor a S_N2 pathway instead.

3° alcohol alkyl halide

lecture 2

p. 297

SOCl₂

py

This reaction works best for primary and secondary alcohols since it proceeds via an S_N2 mechanism. For bromination, instead use PBr₃ · Et₂O at 35 °C.

1° alcohol alkyl halide

2° alcohol alkyl halide

lecture 2

p. 299

Mg

Et₂O or THF

The resulting compound absolutely needs to always be handled in an aprotic solvent (e.g. Et₂O or THF) or it will break. This also means that Grignard reagents can't be prepared from alkyl halides that contain functional groups that would protonate them (e.g. −OH, −NH₂, −CO₂H).

alkyl halide Grignard reagent

lecture 2

p. 299

H₂O

This is what happens if you allow a Grignard reagent to get protonated.

Grignard reagent alkane

lecture 2

p. 302

R'−B(OH)₂

Pd catalyst, K₂CO₃

Suzuki-Miyaura reaction. This reaction is really useful for creating biaryl compounds.

alkyl halide alkane

aryl halide alkylbenzene

lecture 2

name reaction

C−C forming

p. 540

1) R'MgX · Et₂O

2) H₂O

ketone 3° alcohol

Grignard reagent 3° alcohol

lecture 2

C−C forming

p. 540

1) R'MgX · Et₂O

2) H₂O

aldehyde 2° alcohol

Grignard reagent 2° alcohol

lecture 2

C−C forming

p. 540

CH₂O

H₂O

Formaldehyde provides the CH₂−OH group here.

Grignard reagent 1° alcohol

lecture 2

C−C forming

p. 482

X₂

FeX₃

Aromatic halogenation. For iodine in particular, use CuCl₂ as a catalyst instead of FeI₃.

arene aryl halide

lecture 6

p. 484

HNO₃

H₂SO₄

Aromatic nitration.

arene nitro compound

lecture 6

p. 485

H₂SO₄ or HSO₃Cl

Δ

Aromatic sulfonylation. No H₂O may be present during this reaction.

arene sulfonic acid

lecture 6

p. 485

dilute H₂SO₄

Δ

Sulfonation is favored by strong acids whereas desulfonation is favored by dilute aqueous acids. This makes SO₃H groups useful as reversible blocking groups at the para position to favor ortho products.

sulfonic acid arene

lecture 6

p. 488

RX

AlCl₃

Friedel-Crafts alkylation. Some important caveats: aryl and vinyl halides don't work, and the presence of amino groups or strong electron-withdrawing groups will also hinder this reaction.

arene alkylbenzene

alkyl halide alkylbenzene

lecture 6

name reaction

C−C forming

p. 488

RCOX

AlCl₃

Friedel-Crafts acylation. A stoichiometric amount of AlCl₃ is required for this reaction.

arene ketone

acid halide ketone

lecture 6

name reaction

C−C forming

p. 508

1) NaOH, H₂O, Δ

2) H₃O⁺

This reaction requires high temperatures, high pressure and the presence of a base since it proceeds via the thermodynamically disfavored benzyne intermediate.

aryl halide phenol

lecture 6

p. 509

1) NaNH₂, NH₃ (l)

2) H₃O⁺

Unlike the reaction to create phenols using a benzyne intermediate, this reaction doesn't require high temperatures.

aryl halide aryl amine

lecture 6

p. 510

KMnO₄

H₂O

This oxidation reaction requires the presence of a benzyllic hydrogen on the alkyl substituent. It also works even in the presence of other substituents.

alkylbenzene carboxylic acid

lecture 6

C−C cleavage

p. 513

H₂, Rh/C

CH₃CO₂H

Pt is another potential catalyst for reducing aromatic compounds, but in this case the reaction requires pressures around 130 atm.

arene alkane

alkylbenzene alkane

lecture 6

p. 511

NBS

hν, CCl₄

Benzylic bromination. In this reaction, a hydrogen atom on a carbon adjacent to a double bond or aromatic ring is replaced with Br.

alkylbenzene alkyl halide

lecture 7

p. 293

NBS

hν, CCl₄

Allylic bromination. In this reaction, a hydrogen atom on a carbon adjacent to a double bond or aromatic ring is replaced with Br.

alkene alkyl halide

lecture 7

KOtBu

Elimantion using tert-butoxide favors the formation of the less substituted alkene, also known as the Hofmann product.

alkyl halide alkene

lecture 7

p. 430

Δ

Diels-Alder reaction. This is a useful reaction for forming cyclic compounds. If the dienophile contains an electron-withdrawing group, the reaction will occur at a high speed. Note that dienes need to be able to adopt an s-cis conformation for this reaction to work, or else the two ends will be too far apart.

diene alkene

lecture 7

name reaction

C−C forming

p. 534

1) BH₃ · THF

2) H₂O₂, NaOH

Hydroboration-oxidation. This reaction yields syn, non-Markovnikov products. Compare and contrast with the hydroboration-oxidation of alkynes covered in Lecture 2. Tetrahydrofuran is the archetypal solvent used for this reaction.

alkene 1° alcohol

alkene 2° alcohol

lecture 8

p. 534

1) Hg(OAc)₂, H₂O

2) NaBH₄

Oxymercuration-demercuration. The addition in this reaction follows Markovnikov's rule.

alkene 2° alcohol

alkene 3° alcohol

lecture 8

p. 534

1) OsO₄, py

2) NaHSO₃, H₂O

Dihydroxylation. This addition reaction yields cis diols. For trans diols, instead use RCO₃H/CH₂Cl₂ followed by H₃O⁺.

alkene diol

lecture 8

m-CPBA

alkene epoxide

lecture 8

p. 535

1. [H^-]

2) H₃O⁺

Typical [H^-] reducing agents include NaBH₄ and LiAlH₄. See also Lecture 2 for a way to form alcohols from carbonyl compounds using Grignard reagents.

aldehyde 1° alcohol

lecture 8

p. 535

1. [H^-]

2) H₃O⁺

Typical [H^-] reducing agents include NaBH₄ and LiAlH₄. See also Lecture 2 for a way to form alcohols from carbonyl compounds using Grignard reagents.

ketone 2° alcohol

lecture 8

p. 544

TsCl

py

Converting alcohols to tosylates makes them excellent leaving groups for S_N1/S_N2 reactions. Note that the conversion to tosylates also retains stereochemistry.

1° alcohol tosylate

2° alcohol tosylate

3° alcohol tosylate

phenol tosylate

diol tosylate

lecture 8

p. 546

H₃O⁺, THF

25 °C

Dehydration of alcohols. Dehydration of alkenes forms the more substituted (and therefore more stable) alkene following Zaitsev's rule. Dehydration can also be carried out through an E2 mechanism using POCl₃ and pyridine, which has the benefit of not requiring acidic conditions.

1° alcohol alkene

2° alcohol alkene

3° alcohol alkene

phenol alkene

lecture 8

p. 549

R'OH

HCl, Δ

Fischer esterification. This reaction uses a strong acid (HCl) as a catalyst.

carboxylic acid ester

1° alcohol ester

lecture 8

name reaction

p. 550

[O]

Common [O] oxidizing agents include KMnO₄, CrO₃, and Na₂Cr₂O₇.

1° alcohol carboxylic acid

lecture 8

p. 550

DMP or PCC

A mild oxidizing agent is needed to not oxidize the 1° alcohol all the way to a carboxylic acid.

1° alcohol aldehyde

lecture 8

p. 550

[O]

Common [O] oxidizing agents include KMnO₄, CrO₃, and Na₂Cr₂O₇.

2° alcohol ketone

lecture 8

p. 555

1) O₂, Δ

2) H₃O⁺

Phenols are synthesized from isopropylbenzene. This reaction also produces acetone as a byproduct.

alkylbenzene phenol

lecture 8

C−C cleavage

p. 558

Na₂Cr₂O₇

H₂O

Oxidation of phenols yields 1,4-benzoquinone, a multifunctional molecule that exhibits properties of both a ketone and an alkene.

phenol ketone

phenol alkene

lecture 8

p. 570

1) NaH, THF

2) R'X

Williamson ether synthesis. First, the alcohol is deprotonated to an alkoxide, then it reacts with a primary alkyl halide through an S_N2 mechanism.

1° alcohol ether

phenol ether

alkyl halide ether

lecture 8

name reaction

p. 573

HX, H₂O

reflux

Ethers are cleaved by strong acids.

ether 1° alcohol

ether phenol

ether alkyl halide

lecture 8

p. 575

Δ

Claisen rearrangement. This is a exothermic, pericyclic reaction that happens at high temperatures. It is specific to allyl-aryl ethers and allyl-vinyl ethers.

ether phenol

ether ketone

lecture 8

name reaction

C−C forming

p. 798

NaCN

alkyl halide nitrile

lecture 9

C−C forming

p. 798

1) LiAlH₄ · Et₂O

2) H₂O

Don't forget that the compound needs to be protonated (e.g. using H₂O) after reduction.

nitrile 1° amine

lecture 9

p. 798

1) SOCl₂

2) NH₃

carboxylic acid amide

lecture 9

p. 798

1) LiAlH₄ · Et₂O

2) H₂O

Don't forget that the compound needs to be protonated (e.g. using H₂O) after reduction.

amide 1° amine

amide 2° amine

lecture 9

p. 799

xs NH₃

NaOH

S_N2 alkylation. This method of alkylation is generally to be avoided because it gives a mixture of products. The result is a mix primarily containing 1° and 2° amines, but also trace amounts of 3° amines and 4° ammonium.

alkyl halide 1° amine

alkyl halide 2° amine

lecture 9

p. 800

1) NaN₃, CH₃CO₂H

2) LiAlH₄ · Et₂O; H₂O

This method creates an azide ion intermediate through an S_N2 reaction. This azide ion can then be reduced and protonated to yield a 1° amines.

alkyl halide 1° amine

lecture 9

p. 798

H₂

Pt catalyst, CH₃CO₂H

Arylamines are prepared by first nitrating the aromatic compound and then reducing the nitro group. If other reducible functional groups are present, use SnCl₂/H₃O⁺ followed by NaOH instead.

nitro compound aryl amine

lecture 9

p. 800

1) C₈H₄KNO₂

2) NaOH, H₂O

Gabriel amine synthesis. This method of synthesizing 1° amines utilizes a potassium phtalamide.

alkyl halide 1° amine

lecture 9

name reaction

p. 801

1) NH₃

2) H₂/Pt (or NaBH₄)

Reductive amination. An imine is obtained after the first step, which needs to be reduced to yield the amine.

aldehyde 1° amine

ketone 1° amine

lecture 9

p. 801

1) R''NH₂

2) NaBH₄

Reductive amination. An imine is obtained after the first step, which needs to be reduced to yield the amine.

ketone 2° amine

1° amine 2° amine

lecture 9

p. 803

NaOH, Br₂

H₂O

Hofmann rearrangement. Note that one carbon atom is lost as CO₂. The similarly named Curtius rearrangement reactions creates 1° amines from acyl azides.

amide 1° amine

lecture 9

name reaction

C−C cleavage

p. 806

NH₃

Nucleophilic acylation. Depending on the kind of amide desired, R'NH₂ or R'₂NH₂ can also be used instead as reagents.

acid halide amide

1° amine amide

2° amine amide

lecture 9

p. 807

1) xs CH₃I

2) Ag₂O, H₂O, Δ

Hofmann elimination of amines. CH₃I is used here to make NH₂^- a better leaving group. As the name of this reaction implies, the major product is the less substituted alkene, also known as the Hofmann product.

1° amine alkene

2° amine alkene

lecture 9

name reaction

p. 812

HNO₂

H₂SO₄

Sandmeyer reaction. Diazonium salts are useful because they are stable compounds that can be substituted with nucleophiles.

aryl amine arenediazonium salt

lecture 9

name reaction

p. 813

HX

CuX

Copper(Ⅰ) halides can be used to create aryl halides from diazonium salts. For iodination, use NaI instead.

arenediazonium salt aryl halide

lecture 9

p. 813

KCN

CuCN

This reaction turns arenediazonium salts into aryl nitriles. These can later be hydrolyzed to create benzoic acids.

arenediazonium salt nitrile

lecture 9

C−C forming

p. 813

H₃O⁺

or NaOH, H₂O

Hydrolysis of nitriles yields carboxylic acids.

nitrile carboxylic acid

lecture 9

p. 813

Cu₂O

Cu(NO₃)₂, H₂O

arenediazonium salt phenol

lecture 9

p. 814

H₃PO₂

Diazonium salts can be reduced to hydrocarbons with hydrophosphorous acid. This provides a method from removing amino group substituents from aromatic compounds.

arenediazonium salt arene

lecture 9

p. 608

1) DIBAH, toluene, -78 °C

2) H₃O⁺

Esters can be reduced to aldehydes with diisobutylaluminum hydride, typically known as DIBAH.

ester aldehyde

lecture 10

p. 608

1) O₃

2) Zn/H₃O⁺

Oxidative cleavage. Ozonolysis of disubstrituted alkenes yields ketones. Monosubstituted alkenes yield aldehydes instead.

alkene ketone

alkene aldehyde

lecture 10

C−C cleavage

p. 610

1) KMnO₄, H₂O, NaOH

2) H₃O⁺

Hot, alkaline KMnO₄ cleaves ketones into carboxylic acids. When applied to cyclic ketones, this provides an easy method for creating dicarboxylic acids.

ketone carboxylic acid

lecture 10

C−C cleavage

p. 614

H₂O

Hydration of ketones. Reversible reaction that forms a geminal diol. This reaction is why ketones like acetone can remove water. It's catalyzed by both acids and bases.

ketone diol

lecture 10

p. 616

R−OH

This is an addition reaction that is feasible for methanol but not for larger alcohols. The principle is similar to that of ketone hydration. The reaction is not stereoselective.

ketone ether

1° alcohol ether

lecture 10

p. 616

HCN

Note the rare formation of a C−C bond and the reduction of the carbonyl group.

aldehyde nitrile

aldehyde 2° alcohol

lecture 10

C−C forming

p. 619

R''NH₂

ketone imine

aldehyde imine

lecture 10

p. 624

H₂N−NH₂

NaOH

Wolff-Kishner reaction. Converts aldehydes or ketones into alkanes by using hydrazine.

aldehyde alkane

ketone alkane

lecture 10

name reaction

p. 626

HO−CH₂CH₂−OH

H₃O⁺, Dean-Stark

Acetals—especially cyclic acetals formed from diols—are useful as protecting groups. A note about terminology: traditionally, acetal referred to such a compound derived from aldehydes, whereas ketal referred to one derived from ketones. Nowadays, acetal has come to be used as a blanket term for both.

aldehyde acetal

ketone acetal

diol acetal

1° alcohol acetal

lecture 10

p. 628

H₃O⁺

Acetals can be hydrolyzed under acidic conditions to yield the original compound.

acetal aldehyde

acetal ketone

lecture 10

p. 630

R''=PPh₃

Wittig reaction. This reaction uses a phosphorium ylide that can be formed from an alkyl halide.

aldehyde alkene

ketone alkene

lecture 10

name reaction

C−C forming

R'₂CuLi

Conjugate addition (aka 1,4-addition). This is a nucleophilic addition reaction that saturates α,β-unsaturated aldehydes or ketones.

ketone alkane

aldehyde alkane

lecture 10

C−C forming

p. 664

CrO₃

H₃O⁺

Oxidation of aldehydes yields carboxylic acids. Note that a proton source is needed as well.

aldehyde carboxylic acid

lecture 11

p. 665

CO₂

H₃O⁺

Carboxylation of Grignard reagents yields carboxylic acids.

Grignard reagent carboxylic acid

lecture 11

C−C forming

p. 668

SOCl₂, benzene

80 °C

Nitriles can be prepared through dehydration of 1° amides.

amide nitrile

lecture 11

p. 670

H₂O

nitrile amide

lecture 11

p. 671

1) R'MgX · Et₂O

2) H₂O

Grignard reagents can be used to turn nitriles into imine anions, which can then be hydrolyzed into ketones.

nitrile ketone

Grignard reagent ketone

lecture 11

C−C forming

p. 689

SOCl₂

CHCl₃

For bromination, use PBr₃ instead.

carboxylic acid acid halide

lecture 11

p. 689

800 °C

Carboxylic acids combine into acid anhydrides under high temperatures, removing water in the process.

carboxylic acid acid anhydride

lecture 11

p. 689

R'X

Carboxylic acids turn into esters upon S_N2 reaction with 1° alkyl halides.

carboxylic acid ester

alkyl halide ester

lecture 11

p. 696

H₂O, NaOH

acid halide carboxylic acid

lecture 11

p. 697

R'COONa

Et₂O, 25 °C

Sodium formate can be used to generate anhydrides from acid halides.

acid halide acid anhydride

lecture 11

p. 697

R'OH

acid halide ester

1° alcohol ester

lecture 11

p. 700

1) R''MgX · Et₂O

2) H₃O⁺

This reaction forms two new C−C bonds in the process.

acid halide 3° alcohol

Grignard reagent 3° alcohol

lecture 11

C−C forming

p. 700

R'₂CuLi

Et₂O

acid halide ketone

lecture 11

C−C forming

[H^-]

acid halide 1° alcohol

lecture 11

p. 702

H₂O

Acid anhydrides are hydrolyzed into carboxylic acids.

acid anhydride carboxylic acid

lecture 11

p. 702

R'OH

acid anhydride ester

1° alcohol ester

lecture 11

p. 702

NH₃

acid anhydride amide

lecture 11

p. 702

[H^-]

Acid anhydrides are first reduced to aldehydes, and then to 1° alcohols.

acid anhydride 1° alcohol

lecture 11

1) R'MgX · Et₂O

2) H₂O

This reaction forms two new C−C bonds in the process.

acid anhydride 3° alcohol

Grignard reagent 3° alcohol

lecture 11

C−C forming

R'₂CuLi

Et₂O

acid anhydride ketone

lecture 11

C−C forming

p. 704

H₂O, NaOH

or H₃O⁺

Esters are hydrolyzed to carboxylic acids. When this reaction is carried out in a basic solution, it's called saponification.

ester carboxylic acid

ester 1° alcohol

lecture 11

p. 707

NH₃

Et₂O

Esters are aminolyzed to form amides.

ester amide

ester 1° alcohol

lecture 11

p. 707

1) LiAlH₄ · Et₂O

2) H₃O⁺

Fully reducing esters yields 1° alcohols.

ester 1° alcohol

lecture 11

p. 709

1) R''MgX · Et₂O

2) H₃O⁺

Esters yield 3° alcohols when reacting with Grignard reagents.

ester 3° alcohol

Grignard reagent 3° alcohol

lecture 11

C−C forming

p. 710

H₃O⁺

Hydrolysis of amides yields carboxylic acids. Acid-catalyzed hydrolysis is preferred because NH₂^- is a poor leaving group.

amide carboxylic acid

lecture 11

p. 731

H₃O⁺

X₂

Acid-catalyzed α-halogenation. The reaction rate is limited by [carbonyl][H⁺] since the enol formation is the rate-limiting step.

aldehyde α-halo ketone

ketone α-halo ketone

lecture 12

p. 733

py

Δ

Dehydrogenation of α-haloketones. This reaction generates α,β‑unsaturated aldehydes or ketones. The more substituted C=C bond is formed.

α-halo ketone alkene

lecture 12

p. 734

1) Br₂, PBr₃

2) H₂O

Hell-Volhard-Zelinsky halogenation. This reaction involves the halogenation of a carboxylic acid at the α carbon. It requires the α carbon to have at least one H atom.

carboxylic acid alkyl halide

lecture 12

name reaction

p. 739

X₂

NaOH

Haloform reaction. This is a base-catalyzed reaction that causes demethylation of an acetyl group.

aldehyde carboxylic acid

ketone carboxylic acid

lecture 12

C−C cleavage

R'X

Alkylation of enolate ions. This S_N2 reaction also works with pseudohalides like tosylates, triflates, and mesylates.

alkyl halide alkane

tosylate alkane

lecture 12

C−C forming

p. 740

1) DEM, NaOEt, EtOH

2) H₃O⁺, Δ

Malonic ester synthesis. In this reaction, diethyl malonate is used to turn an alkyl halide into a substituted acetic acid. Note that the reaction ends up extending the carbon chain by two carbons. Despite its name, it does not produce esters.

alkyl halide carboxylic acid

ester carboxylic acid

lecture 12

C−C forming

p. 743

1) EAA, NaOEt, EtOH

2) H₃O⁺, Δ

Acetoacetic ester synthesis. This reaction uses ethyl acetoacetate to extend a carbon chain by three carbon atoms.

alkyl halide ketone

ester ketone

lecture 12

C−C forming

p. 760

R''=O

Na⁺ ^-OEt, EtOH

Aldol condensation. The acceptor compound needs to lack α-hydrogens next to its carbonyl group for this reaction. The two α-hydrogens from the donor compound form H₂O with the acceptor compound oxygen, leading to a dehydration.

ketone alkene

aldehyde alkene

lecture 13

C−C forming

p. 764

1) Na⁺ ^-OEt, EtOH

2) H₃O⁺, Δ

Claisen condensation. This reaction forms a β‑keto ester from two esters. RO^- ends up being the leaving group.

ester β‑keto ester

ester 1° alcohol

lecture 13

name reaction

C−C forming

p. 770

R''−CH=CH−COH

H₃O⁺

Michael addition reaction. This reaction requires a very stable enolate ion (e.g. from a β‑keto ester) and an unhindered α,β‑unsaturated aldehyde or ketone.

β‑keto ester aldehyde

aldehyde β‑keto ester

lecture 13

name reaction

C−C forming

p. 773

R''₂NH

Stork reaction. This reaction requires the presence of a hydrogen atom on the α carbon.

ketone enamine

2° amine enamine

lecture 13

name reaction

p. 776

CH₃−COCH=CH₂

Na⁺ ^-OEt, EtOH

Robinson annulation. Combines a Michael reaction with an aldol reaction to form cyclic compounds. The reaction is shown here using 3-buten-2-one, but other α,β‑unsaturated ketone acceptors can be used as well.

β‑keto ester ester

β‑keto ester ketone

lecture 13

name reaction

C−C forming

p. 879

1) Br₂, PBr₃

2) H₂O; 3) NH₃

Hell-Volhard-Zelinsky amination. One way to create amino acids is to combine the previously learned Hell-Volhard-Zelinsky halogenation with an additional nitration step. However, this leads to a racemic mixture of products, which is no good since proteins are made up exclusively of ʟ-amino acids in eukaryotes.

carboxylic acid amino acid

lecture 14

name reaction

p. 880

1) Na⁺ ^-OEt, EtOH

2) RX; 3) H₃O⁺, Δ

Amidomalonate synthesis. This is a modified version of the malonic ester synthesis, where the R part of the alkyl halide becomes the side chain of the amino acid. A racemic mixture of products is obtained.

ester amino acid

alkyl halide amino acid

lecture 14

C−C forming

C−C cleavage

p. 880

1) NH₃

2) NaBH₄, EtOH

Reductive amination of α-keto acids. This reaction was also discussed during Lecture 9 and is here applied to help create amino acids. A racemic mixture of products is obtained.

ketone amino acid

lecture 14

1) NH₃

2) HCN; 3) H₃O⁺

Strecker synthesis. This way of forming amino acids uses an aldehyde, ammonia, and cyanide. A racemic mixture of products is obtained.

aldehyde amino acid

lecture 14

name reaction

C−C forming

p. 880

1) H₂, Rh catalyst

2) NaOH, H₂O

Chiral hydrogenation. Also known as asymmetric hydrogenation. This reaction is enantioselective owing to the chirality of the reagent.

enamine amino acid

lecture 14

p. 975

R−OH

Retro-Claisen condensation. This reverse Claisen condensation reaction is used to cleave the fatty acid chain in the final step of β‑oxidation. When carried out by biological organisms, CoA−SH is used instead of an alcohol.

β‑keto ester ester

1° alcohol ester

lecture 15

name reaction

C−C cleavage