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Major Reaction

Subreaction
Hydrohalogenation

Electrophilic Addition
Hydration

Halogenation

Bromohydrin formation

Catalytic Hydrogenation

REDOX
Cis Hydroxylation

Oxidative cleavage

Epoxide formation

Catalytic Hydrogenation

Catalytic Hydrogenation

Deprotonation of terminal alkyne

Substitution

Sn1

Sn2

Elimination

E1

E2

Reduction

reactions of alcohols

oxidation

oxidation

oxidation

ether synthesis

t-butyl ether synthesis

E1, dehydration

reactions of ethers

ether cleavage

Conversion of alcohol to alkyl halide or tosylate Synthesis of alkyl bromides

Synthesis of alkyl chlorides

Synthesis of tosylates

Reversible additions to aldehydes and ketones

hemiacetals/acetals formation

imine formation

Synthesis of amines

Imines

Alcohol Synthesis

Grignard

Grignard

Grignard

Grignard

Grignard

Reactions of carboxylic acids

formation of acid chloride

formation of anhydride

esterification

hydrolysis

reactions of acid chloride (anhydrides)

hydrolysis
hydrolysis
esterification
formation of amide

reactions of esters

Hydrolysis
synthesis of alcohols
synthesis of alcohols

reactions of amides

Hydrolysis
Reduction

Synthesis of nitriles

SN2

Reactions of nitriles

hydrolysis
reduction

-Halogenation
synthesis of carboxylic acids
Reactions at the a-position of carbonyls

Haloform
Aldol
Claisen
Acetoacetic Ester Synth.
Malonic Ester Synth.
Michael reaction
Robinson Annulation

Acid/base chemistry

formation of enolate
formation of enols

oxidation chemistry
Electrophilic Aromatic Substitution

formation of trans diols


Halogenation
Nitration
Sulfonation
Alkylation
Acylation
Side chain oxidation
reduction of nitroaromatics

REDOX

Starting Material

Reagent

Product

Alkene

HX, ether

Alkyl halides

Alkene

H3O+

Alcohols

Alkene

Br2/CH2Cl2 or CCl4

trans-1,2 dibromides

Alkene

Br2/water

trans-1,2 bromohydrins

Alkene

H2, Pd/C

Alkanes

Alkene

OsO4

cis-1,2 diols

Alkene

KMnO4, H3O+

ketones or acids

Alkene

mcpba

epoxides

Alkynes

H2, Pd/C

alkanes

Alkynes

H2, Lindlar catalyst

cis alkenes

Alkynes

NaNH2

Acetylide anion

2o or 3o alkyl halide

weak nucleophile (may be solvent)

Racemic mixture if substrate is chiral

methyl, 1o or 2o alkyl halide

good nucleohile

Inversion of Configuration

2o or 3o alcohol

weak bases

Alkene @ most substituted C

alkyl halide

Strong base (bulky bases are better) Alkene/Alkyne @ most substituted C

Aldehydes

a. NaBH4/MeOH or a. LAH b.H3O+

1 Alcohol

Ketones

a. NaBH4/MeOH or a. LAH b.H3O+

2 Alcohol

Carboxylic acids & derivatives

a. LAH b. H30+

1 Alcohol

1 Alcohol

PCC

Aldehydes

2 Alcohol

PCC or CrO3

Ketone

1 Alcohol

KMnO4 or CrO3

Carboxylic Acid

alkoxide and alkyl halide

ethers

1o or 2o alcohol

isobutylene gas, acid catalyst

t-butyl ether

2o or 3o alkyl halide or alcohol

H2SO4 or H3PO4

alkene

ether

HBr or HI (conc)

alkyl bromide or iodide/alcohol

t-butyl ether

CF3CO2H

alcohols

Alcohols

PBr3

Alkyl Bromides

Alcohols

SOCl2

Alkyl Chlorides

Alcohols

tosyl chloride

tosylates

Aldehyde or Ketone

Alcohol, H+

hemi acetal or acetal

Aldehyde or Ketone

1o amine, H+

imine

H2 and Pd/C OR NaBH4

Amines

Ethylene Oxide

a. RMgBr/ether b. H30+

1 Alcohol w/ 2 C's

Aldehydes

a. RMgBr/ether b. H30+

2 Alcohol

Formaldehyde

a. RMgBr/ether b. H30+

1 Alcohol w/ 1 C

Ketones

a. RMgBr/ether b. H30+

3 Alcohol

CO2

a. RMgBr/ether b. H30+

Carboxylic Acid

Carboxylic Acid

SOCl2

Acid Chloride

Acid Chloride

Carboxylate Anion

Anhydride

Carboxylic Acid and alcohol

acid catalyst

ester

Amide

Hydrolysis

Carboxylic Acid/Amine

Acid Chloride
Anhydride
acid chloride
Acid Chloride

H2O
H2O
Alcohol
Amine

Carboxylic Acid
Carboxylic Acid
ester
Amide

ester
ester
ester

acid or base
a. LAH b. H30+
a. RMgBr/ether b. H30+

Carboxylic Acid & Alcohol


1 Alcohol
3 Alcohol

amide
amide

acid or base
a. LAH b. H30+

Carboxylic acid & amine


amine

methyl, 1o or 2o alkyl halide

NaCN

Nitrile

nitrile
nitrile

acid or base
a. LAH b. H30+

carboxylic acids
Amines

Ketone or aldehyde
methyl ketone

X2 /HX
I2, NaOH

-Halogenated aldehyde or ketone


Carboxylate Anion

aldehydes and ketones


esters
-keto ester
-di ester
,-unsaturated compound & nucleophile

a. NaOH(cat) EtOH b. neutralize


a. RO- b. H30+
a. NaOEt, EtOH; R-X, c. H30+, Heat
a. NaOEt, EtOH; R-X, c. H30+, Heat
depends

,-unsaturated compound (enone or enal)


-keto ester
Substituted Ketones
Substituted Acids
new bond at carbon

carbonyl compound with a-hydrogen


carbonyl compound with a-hydrogen

base
acid

enolate
enol

alkene
a. mcpba, b. aqueous acid or base
Aromatics
X2, FeX3 OR AlX3
Aromatics
HNO3/H2SO4
Aromatics
H2SO4/SO3
Aromatics
3o alkyl halide, FeX3
Aromatics
RCOCl, FeCl3 OR AlCl3
Aromatics w/ at least 1 benzylic hydrogen KMnO4
nitroaromatics
H2, Pd/C OR iron and tin reagents

trans diol
halogenated aromatic
nitrated aromatic
sulfonated aromatic
alkylated aromatic
acylated aromatic
benzoic acids
Anilines

acidic

Conditions

Mechanism
yes

acidic

yes

neutral

yes

neutral

yes

neutral

no

basic

no

acidic

no

neutral

no

neutral

no

neutral

no

basic

yes

neutral or acidic

yes

neutral or basic

yes

neutral or acidic

yes

neutral or basic

yes

no

no

no

no

no

no

basic

yes

acidic

yes

acidic

yes

acidic

yes

acidic

yes

no

no

no

yes

yes

no

basic

yes

basic

yes

basic

yes

basic

yes

basic

yes

no

yes

acidic

yes

acidic or basic

yes

yes
yes
yes
yes

yes
no
yes
yes
no
yes
yes
no

Acidic
Basic

no
no

(enone or enal)

yes
yes
yes
yes
yes

basic
acidic

yes
yes

either
acidic
acidic
acidic
acidic
acidic
neutral

yes
yes
yes
yes
yes
no
no

Notes

Unimolecular; two step where RDS is formation of carbocation; substrate must be able to form cation (2 o or 3o)

Bimolecular; one step; 1o or 2o substrates

Unimolecular; two step where RDS is formation of carbocation; substrate must be able to form cation (2 o or 3o)

Bimolecular; one step

selective oxidation

a SN2 reaction where the nucleophile is an alkoxide

a reversible reaction that can serve to "protect an alcohol"

a specific E1 reaction

ethers are susceptable to strong acids

a way of "deprotecting" a tert-butyl ether to revieal an alcohol

converting a poor leaving group into a good leaving group

converting a poor leaving group into a good leaving group

converting a poor leaving group into a good leaving group

Water must be removed during the reaction; only cyclic hemiacetals are stable.

Water must be removed; can be reduced to amine

another synthesis of amines

epoxide ring opening

will not tolerate acidic functional groups or solvents

will not tolerate acidic functional groups or solvents

will not tolerate acidic functional groups or solvents

will not tolerate acidic functional groups or solvents

susceptible to hydrolysis

susceptible to hydrolysis

Fisher esterification

must use two equivalent of amine

under basic conditions, reaction is called saponification and results in a carboxylate


Grignard reagent will add twice onto carbonyl center of an ester

nitriles can be installed using SN2 chemistry and hydrolyzed to acids

can be substrate for SN2 or eliminated to give a,b-unsaturated compound


limited in scope, but good to know in order to understand pKa/equilibrium
Intermediate is -hydroxyaldehyde or -hydroxyketone that dehydrates; can be self or mixed condensations
can be self or mixed condensations
can be inter or intramolecular; second step is SN2 and substrate can't be hindered
can be inter or intramolecular; second step is SN2 and substrate can't be hindered
nucleophiles are enolate, thiol, or amine; also called 1,4 conjugate addition
a Michael reaction followed by an aldol

enolates can be nucleophilic


enols in equilibrium with their keto form
epoxide ring opening

only alkyl halides that form stable carbocations may be used


may oxidize multiple side chains

or

or

or

or

or

or

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