CHM 238 All Major Reactions

All important reactions from OChem 1 and 2

HX

alkene

Markovnikov addition of X

1. O3

2. DMS or Zn, acid

alkene

• Ketone on more subbed

• Aldehyde on less subbed

1. OsO4

2. NaHSO3, H2O

alkene

syn addition of diol

KMnO4, NaOH, cold

alkene

syn addition of diol

1. RCO3H (peroxyacid, i.e. mCPBA)

2. H3O+

alkene

1. epoxidation

2. acid-catalyzed ring opening

anti addition of diol

Br2, H2O

alkene

• Halohydrin addition

• OH adds to more subbed

Br2

alkene

dibromination

H2, Pt

alkene

Reduction of pi bond

1. BH3, THF

2. NaOH, H2O2

alkene

• Hydroboration oxidation

• Anti-Markovnikov addition of alcohol

H3O+

alkene

Markovnikov addition of alcohol

1. Hg(OAc)2, H2O

2. NaBH4

alkene

• Oxymercuration reduction

• Markovnikov addition of alcohol

HBr, ROOR (peroxide)

alkene

Anti-Markovnikov addition of Br

NaOH

primary alkyl halide

substitute X for OH

DBU or DBN or t-BuOK

primary alkyl halide

alkene

NaOCH3

primary alkyl halide

ether

NaSH

primary alkyl halide

thiol

CH3CO2Na

primary alkyl halide

ester

NaCN

primary alkyl halide

nitrile

HX (1 equiv.)

terminal alkyne

• Markovnikov addition of X

• alkene

HgSO4, H2SO4, H20

terminal alkyne

ketone

1. R2BH

2. H2O2, NaOH

terminal alkyne

• aldehyde

• Anti-Markovnikov addition of O

X2 (1 equiv.), CCl4

terminal alkyne

dihalogenation

xs X2, CCl4

terminal alkyne

tetrahalogenation

1. O3

2. H2O

terminal alkyne

Carboxylic acid + CO2

1. NaNH2

2. R-X

terminal alkyne

• Retention of alkyne (now internal)

• Addition of R

Na, NH3 (l)

internal alkyne

trans alkene

H2, Pt

internal alkyne

alkane

H2, Lindlar’s cat.

internal alkyne

cis alkene

1. xs NaNH2

2. H2O

vicinal or geminal dihalide

terminal alkyne

xs HX

terminal alkyne

geminal dihalide

SOCl2, pyr.

primary or secondary alcohol

• SN2 replacement of OH with Cl

• inversion of configuration

HCl, ZnCl2

primary or secondary alcohol

• SN2 replacement of OH with Cl

• inversion of configuration

conc. H2SO4, heat

tertiary alcohol

alkene via E1

1. TsCl, pyr.

2. NaOEt

primary or secondary alcohol

1. tosylate intermediate

2. alkene via E2

Na2Cr2O7, H2SO4, H2O

secondary alcohol or phenol

ketone

HBr

primary or secondary alcohol

• Bromination via SN2

• inversion of configuration

1. TsCl, pyr

2. NaBr

primary or secondary alcohol

• Bromination via SN2

• inversion of configuration

PBr3

primary or secondary alcohol

• Bromination via SN2

• inversion of configuration

Na2Cr2O7, H2SO4, H2O

primary alcohol

carboxylic acid

PCC, CH2Cl2

or DMP, CH2Cl2

or 1. DMSO, (COCl)2

2. Et3N

primary alcohol

aldehyde

mCPBA

alkene

epoxide

1. NaOR

2. H3O+

epoxide

• ether

• Nu- on less subbed

1. NaCN

2. H3O+

epoxide

• nitrile

• Nu- on less subbed

1. NaSR

2. H3O+

epoxide

• thioether

• Nu- on less subbed

1. RMgBr

2. H3O+

epoxide

addition of R on less subbed

1. LAH

2. H3O+

epoxide

addition of H on less subbed

HX

epoxide

addition of X on more subbed

[H+], H2O

epoxide

addition of OH on more subbed

[H+], ROH

epoxide

• ether

• addition of OR on more subbed

NaOH, NaH

alcohol

alkoxide (RO-)

NaBH4, NaOH

or H2, Pd/c

or 1. LAH

2. H3O+

aldehyde

primary alcohol

1. NaBH4

2. MeOH

or H2, Pd/c

or 1. LAH

2. H3O+

ketone

secondary alcohol

1. xs LAH

2. H3O+

carboxylic acid or ester

primary alcohol

1. RMgBr

2. H3O+

ketone

• tertiary alcohol

• addition of R to carbonyl C

1. xs RMgBr

2. H3O+

ester

• tertiary alcohol

• double addition of R to carbonyl C

TMS-Cl

alcohol

addition of TMS protecting group to O

TBAF

R-O-TMS

reduction of protecting group

t-BuOK

allyl halide or vicinal dihalide

conjugated diene

HBr

conjugated diene

• single halogenation

• 1,2 and/or 1,4 adduct

Br2

conjugated diene

• allyl dihalide'

• 1,2 and/or 1,4 adduct

heat

diene + dienophile

• cyclohexene

• conservation of configuration

NaOEt, EtOH

ester

beta-keto ester

Na2Cr2O7, H2SO4, H2O

benzylic C

• benzoic acid

• reduction of rest of alkyl chain

1. KMnO4, H2O, heat

2. H3O+

benzylic C

• benzoic acid

• reduction of rest of alkyl chain

H2O

tertiary benzylic alkyl halide

tertiary benzylic alcohol via SN1

NaOH

primary or secondary benzylic halide

primary or secondary benzylic alcohol via SN2

NBS, heat

benzylic H

free-radical bromination at benzylic position

conc. H2SO4

tertiary benzylic alcohol

alkene at benzylic position

NaOEt

tertiary benzylic bromide

alkene at benzylic position

3 H2, Ni, 100atm, 150C

benzene

cyclohexane

Na, CH3OH, NH3

benzene with e-donating substituent

• carbons adjacent to substituent reduced

• cyclohexadiene with substituent

Na, CH3OH, NH3

benzene with e-withdrawing substituent

• carbon attached to substituent reduced

• cyclohexadiene with substituent

Br2, FeBr3

benzene

bromobenzene

Cl2, AlCl3

benzene

chlorobenzene

HNO3, H2SO4

benzene

nitrobenzene (benzene with NO2 substituent)

Zn, HCl

nitrobenzene

aniline (benzene with NH2 substituent)

fuming H2SO4

benzene

• addition of SO3H (benzenesulfonic acid)

• reversible with dilute H2SO4

CH3Cl, AlCl3

benzene

• methylbenzene

• Friedel-Crafts Alkylation

acid halide, AlCl3

benzene

• addition of O=C-R

• Friedel-Crafts Acylation

Zn, Hg, Hcl

benzylic carbonyl

reduction of carbonyl to alkane substituent

H+, H2O

ketone/aldehyde

gem-diol (two alcohols on same C)

H+, ROH

ketone/aldehyde

acetal

H+, HO(CH2)2OH

ketone/aldehyde

cyclic acetal (protecting group)

H+, RNH2 (primary amine)

ketone/aldehyde

imine (R2C=N-R)

H+, R2NH (secondary amine)

ketone/aldehyde

enamine (alkene adjacent to secondary amine)

H+, H2N-NH2 (hydrazine)

ketone/aldehyde

hydrazone (R2C=N-NH2)

NaOH, H2O2, heat

hydrazone

• alkane

• Wolff-Kishner reduction

RMgBr, H3O+

ketone/aldehyde

• tertiary/secondary alcohol

• R adds to carbonyl C

KCN, HCN

ketone/aldehyde

cyanohydrine (geminal alcohol and nitrile)

H2C=PPh3

ketone/aldehyde

• new C=C double bond

• Wittig

RCO3H

ketone/aldehyde

ester

1. NaCN

2. H3O+, heat

alkyl bromide

1. nitrile

2. carboxylic acid

1. Mg

2. CO2

3. H3O+

alkyl bromide

1. Grignard

2. carboxylic acid

1. xs LAH

2. H3O+

carboxylic acid

• primary alcohol

• C=O completely reduced

BH3-THF

carboxylic acid

• primary alcohol

• C=O completely reduced

xs NH3

acid halide

primary amide

xs RNH2

acid halide

secondary amide

xs R2NH

acid halide

tertiary amide

1. xs LAH

2. H3O+

acid halide

primary alcohol

1. LiAl(OR)3H

2. H3O+

acid halide

aldehyde