All Reactions

SN2 reagent, solvent, other

strong nucleophile, polar aprotic, inversion of sterochemistry

SN1 reagent, solvent, other

weak nucleophile, polar protic, rearrangements possible

E2 reagent, solvent, other

strong base, polar protic + heat, antiperiplanar required, Zaitsev or Hofmann product

E1 reagent, solvent, other

weak base, polar protic solvent + heat, rearrangements possible, Zaitsev product

Polar protic solvents

H₂O, ROH, NH₃

Polar aprotic solvents

DMSO, acetone, THF

Weak nucleophile

H₂O, ROH

Strong nucleophile

N₃^-, CN^- , HO^-, RO^-

Strong bases

HO^-, RO^-, H₂N^-, R₂N^-

Weak bases

H₂O, ROH

Big bulky base

E2 favoured

t-buOK, DBU, DBN, LDA, NaH, triethylamine

Br₂/

hv or heat

to alkene

Br added to most substituted H

Regioselective

Cl₂/

hv or heat

to alkene

adds Cl where there's an available H

not regioselective

NBS/

hv or heat

to benzene w/ methyl

replaces benzylic H with Br

hv or heat

to ring diene and ring dienophile

two ring structure formed

endo and exo products

NBS/

hv or heat

to alkene

replaces allylic H with Br

can have multiple products (major product most substituted)

hv or heat

to diene and trans dienophile

two products formed

hv or heat

to diene and cis dienophile

meso product formed

HNO₃/

H₂SO₄

to benzene ring

attaches -NO₂ to benzene

SO₃/

H₂SO₄

to benzene ring

adds -SO₃H to benzene

Cl₂/

AlCl₃

to benzene

add Cl to aromatic ring

Br2/

FeBr₃

to benzene ring

adds Br to benzene

R-X/

AlCl₃

to benzene ring

adds -R to aromatic ring

*can rearrange

ortho/meta/para reagents

Br₂/Cl₂

AlCl₃/FeBr₃

Zn/Hg,

HCl, heat

to ketone

Carbonyl to alkane

Clemmenson Reduction

H₂NNH₂,

-OH, heat

to ketone

Carbonyl to alkane

Wolff-Kishner Reduction

1) KMnO₄, OH^-, heat

2) H₃O+

benzene w/ benzylic hydrogen

adds carboxylic acid at benzylic position, cuts off the rest

R-X/

AlCl₃

to benzene w/ NO₂

No reaction!

R-X/

AlCl₃

to benzene w/ amine

No reaction!

CO, HCl/

AlCl₃

to benzene

adds aldehyde to benzene

Sn, HCl

to benzene w/ NO₂

replace NO₂ with NH₂

NaNO₂, HCl

benzene w/ NH₂

Diazonium formation to make something else!

H₃PO₂

to diazonium

replaces ion with H

KI

to diazonium

replaces ion with I

1. HBF₄

2. heat

to diazonium

replaces ion with F

H₂SO₄/

H₂O, heat

replaces ion with -OH

CuCN or CuBr or CuCl

to diazonium

replace ion with CN, Br, Cl

acid chloride/

AlCl₃

_{to benzene}

adds ketone to benzene (no Cl)

HBr (or HCl, HI)

to alkene

add Br and H (Br more sub)

Rearrangements possible

H3O+

to alkene

add -OH* and H (-OH more sub)

Rearrangements possible

H+, ROH

to epoxide

add -OR* and H (to the O, so makes -OH)

Rearrangements possible

Br₂ or Cl₂/

CCl4

to alkene

Add 2 Br

Anti

Br₂ or Cl₂/

H₂O

to alkene

add Br and -OH*

Anti, + En

Br₂ or Cl2/

ROH

to alkene

add Br and -OR*

Anti, + En

1) Hg(OAc)₂, H₂O

2) NaBH₄

to alkene

Add H and -OH*

Anti, + En

1) Hg(OAc)₂, ROH

2) NaBH₄

to alkene

add H and -OR*

Anti

1) BH₃ • THF

2) H₂O₂, -OH, H₂O

to alkene

add -H* and -OH

Syn

H₂,

Pd/C or Pt/C

to alkyne, alkene

adds 2 H, syn

Alkene → Alkane

Alkyne → Alkane

HBr/

ROOR (peroxide)

to alkene

adds H* and Br

mCPBA or RCO₃H

to alkene

adds syn epoxide ring across double bond

1. RCO₃H (MCPBA)

2. H₃O⁺

to alkene

Adds 2 -OH

Anti

1) OsO₄

2) H₂O₂

to alkene

Adds 2 -OH across alkene

Syn

KMnO4 (cold, dilute)

alkene

Adds 2 -OH across alkene

Syn

1. O₃

2. (CH₃)₂S or Zn/H₂O

to alkene

cleaves alkene =

1º -> aldehyde

2º -> ketone

Reducing cond.

1) O₃

2) H₂O₂

to alkene

cleaves alkene =

1º carboxylic acid

2º ketone

Oxidizing cond.

1. KMnO₄ (hot, concentrated)/

2. H₃O⁺

to alkene

cleaves alkene =

1º carboxylic acid

2º ketone

Oxidizing cond.

H₂,

Lindlar's catalyst

to alkyne

Cis-alkene

Na or Li,

NH₃ (l)

to alkyne

Trans-alkene

1) Sia₂BH THF

2) H2O2, OH-, H2O

to terminal alkyne

Aldehyde terminal C (Less sub)

HgSO₄/

H₂SO₄, H₂O

to internal alkyne

2 products: Ketones added to each alkyne carbon

1. NaNH₂,

2. R-X

to alkyne

Adds alkyl chains

SN2

1. NaNH₂,

2. Ketone, H₃O⁺

to alkyne

Adds to tertiary side -OH + 2 CH₃

_SN2

ROH/

H+

to alkene

Add -OR* and -H

Rearrangement possible

HgSO₄/

H₂SO₄, H₂O

to terminal alkyne

Adds ketone to more sub

HBr

to terminal alkyne

1 equiv: Br more sub alkene

2 equiv/xs: 2 Br more sub alkane

HBr

to internal alkyne

1 equiv: Br to either side of alkene

2 equiv/xs: 2 Br to either side (they just have to be together)

Br₂/

CCl₄

to alkyne

1 equiv: 2 Br to each side of alkene

2 equiv/xs: 4 Br everywhere

1. O₃

2. H₂O

to terminal alkyne

1 carboxylic acid and 1 CO₂

1. O₃

2. H₂O

to internal alkyne

Two carboxylic acids (same product if symmetrical)

Zn/Hg, HCl/

heat

to ketone

Remove carbonyl

Clemmenson Reduction

H₂NNH₂, OH^-/

heat

to ketone

Removes carbonyl

Wolff-Kishner Reduction

Na₂Cr₂O₇ or H₂CrO₄ or KMnO₄

CrO_3/H₂SO₄

to alcohol, aldehyde

Makes carboxylic acids when it can or ketones

1º alcohol -> carboxylic acid

aldehyde -> carboxylic acid

2º alcohol -> ketone

NEVER 3º

strong oxidizer

PCC or 1. DMCO, (COCl₂) 2. NEt₃

to alcohol

turns -OH to carbonyl

1º alcohol -> aldehyde

2º alcohol -> ketone

NEVER 3º

weak oxidizers

NaBH₄/

EtOH/MeOH/H₂O

to ketone, aldehyde

ketone → 2º alcohol

aldehyde → 1º alcohol

weak reducer

H₂O/

H₃O⁺ or OH^-

to ketone, aldehyde

ketone -> geminal diol

1. RO^-

2. ROH

to ketone, aldehyde

makes hemi acetal/ketal

basic conditions

1. ROH

2. H+ or acid catylst

to ketone, aldehyde

reverse it?

makes acetal/ketal

acidic conditions

H₃O⁺ is used to reverse

ethylene glycol

to ketone, aldehyde

reverse it?

ketone/aldehyde -> cyclic ketal/acetal

functions as a protecting group for ketones and aldehydes

H₃O⁺ is used to reverse

RNH₂/

H₃O+

to ketone, aldehyde

reverse it?

makes imine via 1º amine

H₃O⁺ is used to reverse

R₂NH/

H₃O+

to ketone, aldehyde

reverse it?

makes enamine via 2º amine

forms double bond on less sub if applicable

H₃O⁺ is used to reverse⁺

R=PPh₃ (phosphylide)/

nBuLi

to ketone, aldehyde

C=O bond --> C=C-R bond

Wittig Reaction

weak reducing agent

NaBH₄

Can only reduce aldehydes and ketones to alcohols

strong reducing agent

LiAlH₄

strong oxidizing agents

Na₂Cr₂O₇ or H₂CrO₄ or KMnO₄

CrO_3/H₂SO₄

weak oxidizing agents

PCC or 1. DMCO, (COCl₂) 2. NEt₃

Can only oxidize alcohols (1º and 2º) to aldehydes and ketones

1) LiAlH₄

2) H₃O+

to ketone, aldehyde

ketone → 2º alcohol

aldehyde → 1º alcohol

strong reducer

1. R-MgX, Et₂O

2. H₃O⁺

to aldehyde

Makes 2° alcohol

1. R-MgX, Et₂O

2. H₃O⁺

to ketone

Makes 3° alcohol

1. 2 eq. R-MgX, Et₂O

2. H₃O⁺

to ester

Makes 3° alcohol @ carbonyl, other O disappears

1. 2 eq. R-MgX, Et₂O

2. H₃O⁺

to acyl chloride

Makes 3° alcohol @ carbonyl, Cl replaced with R

1. R-MgX, Et₂O

2. H₃O⁺

to epoxide

R adds to less sub

1. CO₂, Et₂O

2. H₃O⁺

to Grignard reagent

Makes carboxylic acid

1. (CH₃)₂CuLi

2. H₃O⁺

SOCl₂/

PCl₃ or (COCl)₂

to carboxylic acid

makes acid chloride

1) LiAlH₄

2) H₃O+

to acid chloride

Makes 1° alcohol

1) LiAlH₄

2) H₃O+

to amide

Removes carbonyl, C conserved

Strong reducer

1. DIBAL-H, -70ºC

2. H₂O

to ester

Cleaves ester to aldehyde

1. LTBA or LiAlH[O(CH₃)₃]₃

2. H₂O

to acid chloride

Cl to H (aldehyde)

Reduction

1. Br₂

2. OH-

to amide

amide -> amine (with loss of a C)

Hoffman Rearrangement

1) LiAlH₄

2) H₃O+

to nitrile

Adds NH₂

Carbon conserved, keep track of it

Strong reducer