Orgo exam 3 reactions

PCC oxidatiion to ketone or aldehyde

Reagent: 1’ alcohol
Conditions: PCC (CrClO3, PH(NH))
Product: ketone/aldehyde

Hydride on aldehyde

Reagents: aldehyde
Conditions: NaBH4, MeOH (acid)

Product: R- -OH

Hydrides on ketone

Reagents: ketone
Conditions: LiAlH4, THF, H3O
Product: C(OH, R, R)

organometallic general mechanism

1
Reagents: R-M, aldehyde
Conditions: THF
Product: O- -(H,R,R’)
2
Reagents: O- -(H,R,R’)
Conditions: H3O
Product: OH - -(R’,R)

organolithium formation

Reagent: R-X
Conditions: Li, THF
Product: R-Li

grignard reagent formation

Reagent: R-X
Conditions: Mg, THF
Product: R-MgX

Condensation on Carbonyls general mechanism

Reagents: ketone/aldehyde, 2Nu-H
Conditions: None
Products: C(Nu, Nu, R, H/R), H2O

Carbonyl condensation with alcohols

Reagents: ketone/aldehyde, 2R’’-OH
Conditions: cat acid, TsOH
Products: C(R’’O, R’’O, R, R/H), H2O

Condensation reactions - 1’ amines

Reagents: ketone/aldehyde, R’-NH2
Conditions: heat, PhMe, cat acid AcOH
Product: imine, H2O

Condensation reactions - 2’ amines

Reagents: ketone/aldehyde, HNR2
Conditions: heat, PhMe, cat AcOH
Products: enamine, H2O

Making carboxylic acid

1 grignard and dry ice (CO2)
2 jones oxidation
Reagents: 1’ alcohol, CrO3
Conditions: H2SO4, H2O, acetone

acid chloride reactions

carboxylate —> OH- excess
amide —> HNR2
ester —> R’-OH
carboxylic acid —> H2O
acid anhydride —> carboxylic acid

acid anhydride reactions

carboxylate —> OH- excess
amide —> HNR2
ester —> R’-OH
carboxylic acid —> H2O
acid chloride —> N/A

carboxylic acid reactions

carboxylate —> OH- (base)
amide —> amide coupling (1/2’ amine/DCC)
ester —> R’-OH, H2SO4, heat
acid anhydride —> N/A
acid chloride —> SOCl2, pyridine

fisher esterification

Reagents: carboxylic acid, R’-OH
Conditions: H2SO4, heat
Product: O=C(R, OR’)

ester reactions

carboxylate —> OH- excess
amide —> HNR2
carboxylic acid —> H3O (reverse fisher esterification)
aldehyde —> DIBAL
rest —> N/A

amide reactions

carboxylate —> OH-, heat, (terrible yield)
ester —> N/A
carboxylic acid —> H3O, excess H2O
rest —> N/A

carboxylate reaction with carboxylic acid

H3O+ (any acid)

organometallic reactions

R-Li, THF, H3O —> all
R-MgX, THF, H3O —> all but carboxylates
RCuLi, THF, H3O —> acid anhydride, acid chlorides
nothing works on carboxylic acids or carboxylates

Organometallic nucleophilic mechanism

Reagent: O=C(R, LG)
Conditions: 2 equiv Nu, H3O
Product: C(OH, R, Nu, Nu)

synthesis of organocuprates

1
Reagents: R-X
Conditions: Li, THF
Product: R-Li
2
Reagents: R-Li
Conditions: CuX
Product: R2CuLi

hydrides reactions

LiAlH4, THF, H3O —> all
NaBH4, MeOH —> ketone/acid anhydride
NaCNBH3, NaBH(OAc)3 —> imine

amide reduction with LiAlH4

Reagent: amide
Conditions: LiAlH4, THF, H3O
Product: R- - NR2 + (Al2O3)

carboxylates with LAH

Reagent: carboxylate
Conditions: LiAlH4, THF, H3O
Product: R- -OH

DIBAL reduction

Reagents: ester, DIBAL reagent
Conditions: THF, -78C, H3O
Product: aldehyde

amide coupling

Reagents: carboxylic acid, 1/2’ amine
Conditions: DCC reagent
Products: amide, urea

synthesis of nitriles

Reagent: O=C(R, NH2)
Conditions: SOCl2
Products: R-CN + SO2 gas

nitriles reactions

carboxylate —> N/A
amide —> H3O+
ester —> N/A
carboxylic acid —> H3O+, heat
1’ amine —> LAH
rest —> N/A

nitriles to amines

Reagent: nitrile
Conditions: LiAlH4, THF, H3O
Products: 1’ amine

wittig reaction

Reagents: ketone/aldehyde, R’ - -PPh3
Conditions: strong base (Li-butanol)
Product: R’ -=(R, H/R) + (O=PPh3)

synthesis of ylide

Reagents: PPh3, alkyl halide
Conditions: Sn2
Product: ylide