Orgo 2 quiz Review compounds/ rxns

i. BH₃ ii. H₂O₂, OH, H₂O

Cis addition anti-Markovnikov, concerted

OsO₄ + H₂O₂

addition concerted, of 2 OH groups along an alkene

H₂+ Pd/c

Hydrosolvation, concerted addition of 2 H’s to an alkene

Br₂

Halogenation, trans addition to an alkene (2Br), bromonium ion intermediate

i. Hg(OAC)₂, H₂O ii. NaBH₄

Oxymercuration/reduction, trans addition of OH markovnikov

H₂O + Br₂

Halohydrin formation, trans addition of OH and Br, bridged halonium ion intermediate, OH on more substituted side

HBr

Addition via carbocation intermediate, of H + Br, Markovnikov

H₂O + H₂SO₄

Addition of H+OH on an alkene via carbocation intermediate, Markovnikov

BH3 + alkyne + H₂O₂

Forms a ketone where an alkyne once was though tautomerization of an alkene and oxygen

H₂, Lindlar’s Catalyst

Alkyne addition of Hydrogen, but stops at alkene

Alkyne + NaNH₂

Carbanion nucleophile formed

TsCl + weak base (such as pyridine)

turns OH into a pseudohalide (good LG) while leaving a Cl ion in solution to chill with pyridine or the other weak base)

SOCl₂

replaces OH group with Cl through SN2 reactions

HBr +Alcohol

replaces OH group with Br through SN2 after making oxygen a good leaving group

2 alcohols + acidic conditions

pinacol rearrangement, forms aldehyde or ketone from carbocation formation from ROH₂ Leaving group

Acid + 3* Alcohol

E1 reaction

HCl + 3*Alcohol

SN1 Reaction

H₃PO₄

Strong acid solution similar to H₂SO₄

Alcohol + NaH

forms Alkoxide making O^- a good nucleophile for SN2

SN2 is hindered by branching

thus SN1 or E1 will occur

2* alcohols + Acid

E1 reaction of alcohol

H₂CrO₄

Fully oxidizes alcohol if 2 H’s are present, making carboxylic acid

DMP

Forms an aldehyde or ketone same as PCC

PCC

forms an aldehyde or ketone same a DMP

Alkoxide + alkylhalide

SN2 Williamson ether synthesis

Alkene + alcohol in acidic conditions

intercepts Carbocation intermediate, for ether synthesis

Epoxide

strained 3 membered cyclic ether

i. Br₂, H₂O ii. NaH

epoxide synthesis using 2 SN2 reactions

RCO₃H

Peracid, able to form epoxides when added to an alkene

mCPBA

a type of peracid that can form epoxides

Basic conditions + Epoxide + nucleophile

nucleophile attacks less substituted carbon of the epoxide SN2

Acidic conditions + epoxide + H₂O

H₂O attacks the carbon that can better stabilize a positive charge (more substituted)

Mg⁰ + alkyl halide

forms Grignard reagent/ carbanion nucleophile for forming larger C-C chain. Not compatible with acidic hydrogen

2Li⁰

Organolithium synthesis same as Grignard, but more reactive forming H₃C-CH₂-Li nucleophile

Aldehydes and ketones are good

electrophiles

Grignard + aldehyde ii. H3O

2* alcohol is formed

Grignard + ketone iiH30

3* alcohol is formed

Grignard + epoxide ii. H30

alcohol on more substituted side with c-c bond forming on less substituted side

What do you need to form an epoxide?

An alkene and a peracid, or adding NaH/NaOH to an alcohol 1 C away from a halogen.

Acetal group consists of

2 OR’s attached to 1 Carbon with a hydrogen attached

Ketal group consists of

2 OR’s attached to 1 carbon with 2 carbons bound to it

Hemiacetal

Intermediate functional group with 1 OH, 1 OR, 1R, and 1 H attached to a carbon

Hemiketal

Intermediate functional group with 1 OH, 1 OR, 2R’s attached to one carbon

imine group

C=N functional group

Tertiary amines

do not react with aldehydes or ketones

RNH2 + aldehyde or ketone forms

an imine with C=N-R

Wittig reagent

Ph₃P=CR₂ which replaces the O=CR₂ Which will form Ph₃P=O and R₂C=CR^’₂

Alkyl substituted Wittig reagent

Prefers Z orientated products

Sp² substituted Wittig reagents (stabilized)

Prefers E orientated products

Wittig reagents + ketone

Slower, less E/Z stereoselectivity

LiAlH₄

Reducing agent, Can turn carboxylic acids into alcohols, and aldehydes into alcohols

NaBH₄

Reducing agent weaker than LiAlH₄, Can turn aldehydes/ketones into alcohols

Adding grignard reagent to any carboxylic acid derivative

Will form a tertiary alcohol by double nucleophilic attack onto the carbon, unless the carboxylic acid derivative is an amide or carboxylate which will yield no reaction.

What happens if you add grignard reagent to an amide or carboxylate?

There will be no reaction

Adding LiAlH4 and and H30 workup to carboxylic acid derivatives

will turn every carboxylic acid derivative into an alcohol, except for amides which will form a single bonded amine.

What happens if you add LiAlH4 to an amide or nitrile group?

you form a primary amine for a nitrile and C-NR2 amine for the amide

Me2CuLi + Esters/Ketones/Aldehydes

No Reaction

Me2CuLi + Acid chlorides

forms a ketone

Grignard + nitrile

Forms a ketone with a N=C intermediate

Weinreb Amides + Grignard or MeLi

Forms a stable tetrahedral intermediate forming a ketone

Dibal Reactivity

more reactive than NaBH4, but less so than LiAlH4, works on every carboxylic acid derivative and aldehydes/ketones, except for amides and carboxylic acids.

Dibal + carboxylic acid derivatives

forms an aldehyde when given 1 equivalent of Dibal to solution, but makes a primary alcohol with 2 equivalents

Form an acid chloride from a carboxylic acid

Use SOCl2

Are amides basic?

No amides are not basic, but amines are

How can you turn any derivative into carboxylic acids

i. NaOH+H2O, ii. H3O and heat + or H2SO4 + H2O and heat

carbodiimide + Carboxylic acid

forms a mixed anhydride intermediate which will then form an amide product.

amine + acid chloride/ anhydrides

forms an amide you need 2 equivalents of amines for the one to be a base for a counterion that is released and one for the addition.

Can you form a carboxylic acid FROM an amide?

yes using acid or base catalyzed hydrolysis

B-Lactam

ring strained amide which is more electrophilic than a regular amide.

Amide + NaOme +MeOH, or Amide + H2NR

No reaction formed not electrophilic enough, need to turn back into carboxylic acid or derivative strong enough

Fischer Esterification

Carboxylic acid + NaOR + Ether + heat forms an ester from a carboxylic acid (fully reversable)

Ester hydrolysis

Hydroxide adds to ester forming a carboxylic acid and HOR alcohol

Saponification

turning natural Esters into alcohols by adding KOH or NaOH

Form an ester from an alcohol using SN2

NaH forms carboxylate O- which attachs I-CH3 forming ester

Diazomethane

turns carboxylic acid into an ester by changing from (-):CH2N2 into N2 gas

What does Wittig do when mixed with an acid/acid derivative

No reaction because Wittig is not strong enough, or it just protonates the Wittig

NaOR + Ketone/Aldehyde

Forms enolate which reacts with the ketone/aldehyde forming a ketone 4 bonds away from an alcohol, can further react to form an E1CB reaction which forms a ketone and an alkene. Only some of ketone/aldehydes form enolates

LDA

Lithium Diisopropylamide, forms 100% enolate from an aldehyde or ketone, or ester. Doesn’t react further because it is hindered, also makes kinetic equivalent because it is bulky.

Enolates require what to form?

A carbonyl + alpha Hydrogens attached to a carbon

can you do an aldol reaction with acidic conditions

yes, forming an enol which then slowly reacts an always condensates the beta-ketoester, into a ketone + alkene

Can Enolates react with other molecules other than ketones/aldehydes/esters

Yes enolates are good nucleophiles and can be brominated, can preform sn2 rxns to add carbons too

Why are esters different for enolate reactions?

Enolates form tetrahedral intermediates, kick out the OR group, and then form a double bond by being deprotonated by the -OR group until acid workup.

Ring sizes you can make from Enolates

5,6,7 (anything else is too strained) especially 4 or 3 membered rings. 5 and 6 are preferred

How to get rid of an ester when conjugated with another carbonyl (decarboxylation)

Add H2SO4 and H2O which will form a ring that kicks out CO2 and forms an enol which goes to an ketone.

Michael Addition

enolate addition to alpha, beta unsaturated carbonyls. Use LDA for the enolate addition with ketones. Can use NaOR for ketoester enolate alkylation and subsequent decarboxylation. 

Can also use enamines to have an alkene preform SN2 on a alkyl halide, and then work up with H3O+ to revert back to a ketone.

What nucleophiles prefers to do a 1,2 addition on carbonyl derivatives with a conjugated alkene?

Grignard reagent, and LiAlH4

What nucleophiles prefers 1,4 addition for conjugated carbonyls

Cuperates, Enolates, and Amines.