Organic Reactions

yay I just LOVE orgo

aldehyde (rxn with formaldehyde isn’t useful), ketone, acid chloride

What carbonyls does NaBH4 react with?

Carboxylic acids and amides

What carbonyls do grignard reagents and organolithium NOT react with?

Aldehydes (and formaldehyde), ketones, acid chlorides, esters, CO2

What carbonyls DO grignard reagants and organolithium react with?

All of them except CO2 and rxn with formaldehyde isn’t useful

What carbonyls des LiAlH4 react with?

An aldehyde

What can a grignard react with to form a 2° alcohol?

Aldehydes and acid chlorides

What can both hydrides react with to form a 1° alcohol?

Esters and carboxylic acids

What can ONLY LiAlH4 react with to form a 1° alcohol?

deprotonation to form a carboxylate anion

What happens when only ONE EQUIVALENT of LiAlH4 is reacted with a carboxylic acid

Acid chloride, esters

What carbonyls have normal leaving groups?

Need to add 2 equivalents

What does having a leaving group mean?

Amides and carboxylic acids

In which carbonyls does O-AlH3 function as the leaving group?

3, LiAlH4

How many equivalents do I need to add to carboxylic acid to turn it into a 1° alcohol? What do these equivalents have to be?

aldehyde

What does a grignard reagent/organal lithum react with to form a 2° alcohol?

A ketone

What can BOTH LiAlH4 and NaBH4 react with to form a 2° alcohol?

A ketone

Which is more unstable a ketone or ester?

Ketones, acid chlorides, esters

What carbonyls can a grignard reagent/organolithium react with to form a 3° alcohol?

hydrides

What type of reagent in carbonyl rxns CAN NOT form a 3° alcohol

React CO2 with a griganrd reagent or organolithium

How to form a carboxylic acid with carbonyls

React an amide with LiAlH4

How to form an amine with carbonyls

formaldehyde

What type of carbonyl when reacted with NaBH4 and LiAlH4 makes not useful products?

No because they’re resonance stabilized and the O is negative (repels the nucleophile)

Do carboxylate anions react with grignard or organolithium?

Deprotonation

What happens when the first equivilent of LiAlH4 is added to a carboxylic acid?

3

How many equivilants on LiAlH4 do you need to add to carboxylic acids to create a primary alcohol

Deprotonation

What happens when grignard, organolithium, and NaBH4 react with carboxylic acids?

2 attached atoms with opposite charges

Defintion of ylides

Ketones and aldehydes

What carbonyls do sulfur ylides react with?

Ketones and aldehydes

What carbonyls do phosphonium ylides react with?

Epoxides

When reacted with ketones and aldehydes what functional group do sulfur ylides form?

Alkenes

When reacted with ketones and aldehydes what functional group do phosphonium ylides form?

Oxygen’s LP

What makes up the 3rd bond in an epoxide formed by a sulfur ylide?

Sulfur dimethyl+(Methyl w/ LG), 1 set of Sulfur LP grabs the C in the methyl group= (positively charged)Sulfur trimethyl+n-butyl lithium (acting as a base)= One of S’s methyl groups loses a H

How to form a sulfur ylide

acid/base

What type of reaction forms ylides

(Pph3+Lp)+ alkyl group with a leaving group+ Lp grab the C (C MUST HAVE AT LEAST 1 H)=alkyl group attached to (positively charged) Pph3 (with the attached C having at least 1 H)+n-butyl lithium which takes a proton

How to form wittig reagents/phosphonium ylides

You can add lots of different alkyl or non-alkyl groups to them to get the product you want

What’s unqiue about phosphonium ylides?

P’s LP

What makes up the new C-P bond in the creation of a P ylide?

No

When attaching a Pph3 group to a carbon group do you gain a C?

The one directly bonded to the positive atom

Which C does n-butyl lithium take the H from (in the formation of ylides)?

The C- (directly bonded to the +atom)

What acts as the nucleophile in ylides?

2

If you create an OH with an epoxide how many Cs away is the nucleophilic C/the new C bond?nucleophilic

1

If you create an OH with a carbonyl how many Cs away is the nucleophilic C/the new C bond?

Gain of bonds to O

Oxidation

Gain of bonds to H

Reduction

reductions

What type of rxn is it when we react hydrides to carbonyls?

primary amines

What do nitriles reacted with LiAlH4 form?

Jones reagent

Chromic acid

Chromic acid

Jones Reagent

Jones/Chromic acid has water, PCC does not

Difference between PCC and Jones/Chromic acid?

oxidations

What type of rxns do Jones and PCC do when reacted with OHs

No rxn

Jones AND PCC with tertiary OH

Ketone

Jones and PCC with secondary OH

Primary

What type of alcohol differs with Jones and PCC

Carboxylic acid

Primary OH with Jones

aldehyde

Primary OH with PCC

Use Jones or PCC to get to a carbonyl

1st step in turning an OH into an alkene or epoxide

Change your OH into a carbonyl to avoid an acid base rxn

What should you do before creating a grignard if an OH is present?

mCPBA

reagent that forms an epoxide THAT IS NOT sulfur ylide

syn addition

type of epoxide addition with mCPBA

Grignards/organolithium and LiAlH4

What can epoxides react with?

React it with 2 eqvs of LiAlH4

How to form amines with a nitrile

An alkene

What does mCPBA react with to form an epoxide?

hydrate

hemiacetal/hemiketal

acetal/ketal

imine

enamine

H2O (water)

What is the nuc for hydrate synthesis?

Alcohol

What is the nuc for hemiacetal/hemiketal synthesis?

Alcohol

What is the nuc for acetl/ketal synthesis?

1 amine

What is the nuc for imine synthesis?

2 amine

What is the nuc for enamine synthesis?

Add water

How to favor the hydrate (product)?

Remove water

How to favor the reactants (ketone/aldehyde) in hydrate synthesis?

remove water

How to favor the acetal/ketal (product)?

add water

How to favor the reactants (aldehyde or ketone) in acetal/ketal synthesis?

An acetal or ketal but with one addition instead of 2 and a deprotonation of that addition

What is a hemiacetal/hemiketal

The catalytic H+

What gives you the proton for protonation in hydrate, acetal, metal, imine, and enamine synthesis?

Water

What acts as your base when you add water?

the OH

What acts as your base when you’re removing water?

to favor acetal, ketal, enamine, and imine synthesis

When do you need to add water?

To favor the formation of aldehydes and ketones from hydrates and to favor the formation of acetals, ketals, imines, and enamines from ketones and aldehydes

When do you need to remove water?

imine

What does a 1° amine +Ketone or aldehyde form?

enamine

What does a 2° amine + ketone or aldehyde form?

remove water

How to favor the imine side?

remove water

How to favor the enamine side?

add water

How to favor aldehyde or ketone synthesis from imines?

add water

How to favor aldehyde or ketone synthesis from enamines?

The N

What atom do we deprotonate from in the final step of imine synethsis?

The C closest to the iminium ion

What atom do we deprotonate in the final step of enamine synthesis?

1° amine

What is the nucleophile in imine synthsis from ketones or aldehydes?

2° amine

What is the nucleophile in enamine synthsis from ketones or aldehydes?

H2N-NH2, KOH, Delta (heat)

Wolff-Kishner reagents

Synthesize amines from iminium ions

What does reductive amination do?

NaBH3-CN+ 1eqv H+

Reductive amination reagent

The C= to the N

Where does the H- from the reductive amination reagent (Na-BH3-CN) attack?

Aldehyde/ketone, cat. H+, (-H2O), 1° amine

Reagents for imine synthesis

Aldehyde/ketone, cat. H+, (-H2O), 2° amine

Reagents for enamine synthesis

aldehyde/ketone, cat. H+, (-H2O), (an OH)

Reagents for Ketal/Acetal synthesis

aldehyde/ketone, cat. H+ (+H2O)

Reagents for hydrate synthesis