Reduction of Carbonyls

Primary Alcohol + PCC/DMP/DMSO/Swern

Aldehyde

Secondary Alcohol + Jones Reagent (Na2Cr2O7/H2SO4,H2O)

Ketone

Primary Alcohol + Jones Reagent (Na2Cr2O7/H2SO4,H2O)

Carboxylic Acid

Terminal Alkyne + R2-BH

O=C on less substituted carbon

Terminal Alkyne + HgSO4, H2O, H2SO4

O=C on more substituted carbon

Internal Alkene + O3

Cleaving, two products (Carbonyl)

Terminal Alkyne + O3

Cleavage, Carboxylic Acid + CO2

Carboxylic Acid + SOCl2

Subs. of OH with Cl (Acid Chloride)

Carboxylic Acid + NaOH/CH3I

Ester + R group bonded to Halogen

EtCl + NaCN/C-CN

Subs. of Cl with CN group (Nitrile)

CH3- + O=C=O

Carboxylic Acid (Add R group, change C=O group to C-OH)

Electronic effect caused by sigma bonds that results partial negative and partial positive atoms in an electrophile

Inductive Effect

Electronic effect caused by pi bonds that results in fully negative or positive atoms and lead to similar atoms with different arrangement of negative/positive atoms and double bonds

Resonance Effect

What has a higher reactivity based on steric effects, Aldehydes or Ketones?

Aldehydes;

more open & reactive

What has a higher reactivity based on electronic effects, Aldehydes or Ketones?

Aldehydes;

due to Inductive effects (partial negative bigger on Aldehyde makes it more reactive)

Which electronic effect is bigger on Carboxylic Acid, Inductive or Resonance?

Resonance

If a tetrahedral intermediate has a Leaving Group (Y=LG), then in basic conditions it will form…

Nucleophilic Acyl Substitution (Nu- for Y)

If a tetrahedral intermediate does not have a Leaving Group (Y=LG), then in basic conditions it will form…

Nu- Acyl Addition (stays tetrahedral, -O gets protonated to OH)

T/F: In acidic conditions, there is no good Nucleophile or Electrophile. For this reason, the Oxygen becomes protonated before the Carbon can be attacked.

True

Least Stable/Most Reactive CA Derivative

Acid Chloride

Most Stable/Least Reactive CA Derivative

Amide

Least to Most Stable CA Derivatives

Acid Chloride > Acid Anhydride > Ester > Amide

T/F: Reactions proceed more easily towards less stable CA Derivatives compared to towards most stable.

False

What groups does NaBH4 reduce?

Aldehydes and Ketones to OH

What groups does LiAlH4 (LAH) reduce?

Any C=O groups

What groups does BH3 * THF reduce?

Only Carboxylic Acid groups

Carboxylic Acid + LiAlH4 (LAH)

First attacks C → second H turns OH to H2O (LG) and is kicked out → third H attacks C once again, No LG→ O- is protonated → Corresponding alcohol

Ester + DIBAH

H attacks C → OMe reacts as a Leaving Group → Aldehyde

Acid Chloride + LiAl(OR)3H

H attacks C → Aldehyde

Et-CN + LAH

Et-Amine

Ketone + H2O (hydration)

Hydrate tetrahedral (not stable)

Hydrate + H2O (dehydration)

Ketone

Acid Chloride + H2O

Carboxylic Acid

Ester + exc. H2O

Carboxylic Acid

What does a Saponification Reaction (NaOH + H3O+) do?

Turns Ester to a Carboxylic Acid, it is how they make soap

Amide + H3O+ & heat

Carboxylic Acid + NH4

What do you use to turn an Acid Halide into an Acid Anhydride?

R-C-O(-), C=O

Ketone + 2eq. CH3OH

Acetal formation

What does an Acetal protect?

Aldehyde

During a reduction

Carboxylic Acid + CH3OH/H+ (acidic environment)

Fischer Esterification

Ester + H2O (must be drying for reaction to drive towards ester)

Carboxylic Acid + 1.NaOH 2. CH3-I

Williamson Ester Synthesis

Ketone + RCO3H (peroxide)

Baeyer-Villagier Oxidation

Ester with insertion of O between Alpha and Beta Carbons

Migratory order for Baeyer-Villagier Oxidation

H > 3°, Ph > 2° > 1° > methyl

What is the product of a carbonyl reaction with the nitrogen nucleophiles NH3 & NH2R?

Imine

What is the product of a carbonyl reaction with the nitrogen nucleophiles NHR2?

Enamine

Ketone + 1. NH2-NH2 2. KOH, H2O

Wolff-Kishner Reduction

Alkane

Ketone + NH3

Imine + H2O

Imine + H2O

Hydrolysis of an Imine or Enamine

ketone + NH3

Acid Chloride + 2 eq. NH3

Amide + NH4+ + Cl-

Acid Anhydride + NH3

Amide + NH4+ + Cl-

What is the product of a reaction with the Grignard reagent (RMgBr) if there is no Leaving Group?

Substitution of a C=O group with an OH and R group

What is the product of a reaction with the Grignard reagent (RMgBr) if there is a Leaving Group?

Substitution of a C=O group with two R groups

T/F: The Gilman Reagent works the same way as the Grignard Reagent but stops before the second addition of the R group when there is a LG.

True

What is the Gilman Reagent?

R2CuLi

Ketone + -CN

Cyanohydrin Formation

creates tetrahedral with OH and CN groups

Ketone + 1. -CN 2. LiAlH4/H2O

Cyanohydrin Formation + Hydrogen Nu- Reduction

Tetrahedral with OH group and CH2+Amine

Ketone + 1. -CN 2. H3O+ & heat

Tetrahedral with OH and CH2+CA

Amide + SOCl2

-CN

CN + H3O+ & heat

Amide

Amide + H3O+ & heat

Carboxylic Acid

Carboxylic Acid + SOCl2

Amide

-CN + Grignard Reagent/H3O+

CN acts as pseudo carbonyl

Creates Ketone

What product does a Wittig reaction form if it is reacted with a ketone and the formula is CH2PPh3?

It substitutes the Oxygen for the CH2 group

Does a Wittig reaction create a Z or E product when its reacted with an EWG?

E

Does a Wittig reaction create a Z or E product when its reacted with a non EWG?

Z

What product does the Horner-Wadsworth Emmons Reaction form?

E

ketone + 2SHR

Thioacetal

works the same way as an acetal group and protects aldehyde group

Ketone + 1. (SH)2H+ 2. Raney Ni

alkane

reduces ketone completely

carbonyl + Zn(Hg)/HCL

alkane

complete reduction

carbonyl+ (H2N)2

alkane

complete reduction