Reactions

Alcohol Reactions

Dehydration H2SO4 R R'' OR R' OH POCl3, pyridine

R R'

R''

(watch for carbocation rearrangements)

R R'

R''

boxed means you will not be responsible for knowing the mechanism

Making alkyl halides H-X, Et2O R OH PBr3, Et2O R OH SOCl2, pyridine R OH TsCl, pyridine R OH R OTs R Cl (for 1 or 2 alcohols) R Br R X (usually 3 alcohols) X = I, Br, Cl

(for 1 or 2 alcohols)

(tosylates behave like halides)

Alcohol Oxidation PCC, CH2Cl2 (1 ) R OH CrO3 H2SO4, H2O R R' (2 ) R OH OH CrO3 H2SO4, H2O R R R' OR O R O water must be absent to stop at the aldehyde stage

OH OR O

K2Cr2O7 H2SO4, H2O

K2Cr2O7 H2SO4, H2O

OR

PCC

R'' (3 ) R' R Not Oxidized by these Cr reagents OH

Ethers Ether Formation 1. NaH 2. R'-X R OH R (subject to the usual considerations for SN2 reactions)

O R'

Williamson ether synthesis

Ether Reactions

(Usually unreactive)

O R'

H-X R X + X R' (X = Cl, Br, I)

Epoxides Epoxide Formation - from alkenes (see below) Epoxide Reactions With strong nucleophiles (basic conditions): O R Nuc R OH Nuc R, etc

Nuc

OR,

attack at the less hindered position (SN2 like)

Under acidic conditions: O R H , NucH R Nuc OH

NucH

H-X, H2O, ROH

attack at the MORE hindered position (SN1 like), inversion of configuration (SN2 like)

Alkene Formation R R' OH R R' X R'' KOH, EtOH R'' H2SO4 R R' R R' R'' R'' dehydration

Alkene Reactions HBr R Br2, CH2Cl2 Br R Br R Br2, H2O HO R H2O, H2SO4 HO R Markovnikov Prod. (less useful method) hydration OH R hydroboration/oxidation anti-Markovnikov Prod. (syn-addition) Br halohydrin formation (also with Cl2 or NBS) (anti addition) Br hydrohalogenation (Markovnikov) halogenation (anti addition) (also H-Cl, H-I)

(also Cl2)

1. BH3-THF 2. H2O2, NaOH, H2O

H2, Pd/C, EtOH H2, PtO2, acetic acid R hydrogenation (syn-addition)

1. OsO4, pyridine 2. NaHSO3, H2O

HO R

OH

(syn-addition) dihydroxylation

epoxidation R

H+, H2O

HO R

OH

(overall anti-addition)

m-CPBA, CH2Cl2 R Br2, H2O HO R Br NaOH, H2O R

epoxidation (syn-addition)

R' R

1. O3, CH2Cl2 2. Zn, acetic acid, H2O R

R'

ozonolysis

Me2S may be used for step 2

Alkyne Formation Br R Br KOH, EtOH R 1. NaNH2, NH3 2. X R' R R double elimination or from Br R Base could also be NaH, BuLi Br

R'

alkylation

(only methyl or 1o halides, and epoxides) Alkyne Reactions Br R

H-Br R

H-Br

Br R

Br hydrohalogenation

Br2, CH2Cl2 R R

Br

Br2, CH2Cl2 Br

Br R Br

Br Br

halogenation

1. BH3-THF 2. H2O2, H2O, NaOH R HgSO4, H2SO4, H2O

R O R

anti-Markovnikov hydration Markovnikov DO need to know keto-enol tautomerism mech.

R' H2, Pd/C, EtOH R R' R 1. Na (or Li), NH3 2. H2O H2, Lindlar catalyst, quinoline R R' Lindlar reduction (a hydrogenation) (syn-addition) R dissolving metal reduction (anti-addition) hydrogenation

reduction

R'

1. O3, CH2Cl2 2. H2O

HO O R + O

R' ozonolysis OH