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Making Alkenes:
1. Elimination of Alkyl Halides: Alkyl Halide conj polyene (zaitsev)
2. Elimination of Alkyl Alcohols: Alkyl Alcohol conj polyene (zaitsev)
3. Alcohol Dehydration with POCl3 (zaitsev) preferred method for alcohols to alkenes
4. Wittig (Hofmann)
a. Ylide formation
Making ketones/aldehydes:
1. Normal Ozonolysis: Alkene
2. Oxidative Ozonolysis: Alkene
3. Oxycope Rearrangement: 1,5 isolated diene/alcohol with heat taut
4. Mild Oxidation: Alcohol using PCC
5. Alkyne Hydrolysis
a. Aldehyde: 9BBN/peroxide, OH, water
b. Ketone: water, acid, Hg2+
6. Alcohols: HIO4 need cis alcohol (1,2 vicinal)
7. Acid Halides
a. Aldehyde = Rosenmunds LiAlH(Ot-Bu)3 selective of acid halides
b. Ketone= Gilmans Cuprate also selective for acid halides
8. Nitriles add across C=N bond and then imine hydrolysis
a. Aldehyde = DIBAL/acid workup
b. Ketone = Grignard/ Acid work up
Making Carboxylic acids:
1. Oxidative Ozonoylsis: Alkene carboxylic acid
2. Strong Oxidation for primary alcohols
3. Medium oxidation on aldehydes
Making alcohols:
1. Reductive ozonolysis: Alkene
2. Hydroboration/Oxidation : Alkene (primary) -hydrogen adds anti Markovnikov
3. Oxymercuration/ Reduction: alkene (tertiary) - hydrogen adds Markovnikov
4. Epoxide opening: Alkene (trans diol) -anti addition
5. Cis- Dihydroxlation: Osmium tetroxide: Alkene (cis diol)
6. Sn2 = tertiary (uses strong base like OH- as base)
7. Sn1 = primary (uses H2O as solvent)
8. Grignard + ketone/aldehydes/epoxides
9. Hydride reductions: carbonyls
10. Reductions: LiAlH4 on cooh (carboxylic acid) , coor (ester), cox (acid halid)
11. Reductions: NaBH4 with aldehydes and ketones
4.
5.
Other:
1. Arthur Cope Reaction
2. Oxycope Reactions
3. Diels-Alder: Cyclohexene product
Claisen Rearrangement
5.. Alcohol reactions: alkyl chloride/bromide, protecting group (TMS-Cl)
6. Acetal/Ketal formation: Weak Nu of Aldehyde/Ketone
a. Can be used as protecting groups when retained in the product
7. Imine formation: Weak Nu of Aldehyde/Ketone
8. Aldoxime Dehydration Oxime Nitrile group + SO2 by-product
9. Grignard Reaction
1.
2.
3.
4.
5.
6.
Tips:
Acid Halide vs. Alkyl Halide
Ozonolysis check - molozonide check - the two carbons attached to oxygens should have the
same substituents as the alkene that formed it
Ozonolysis check - ozonide check- substituents off the carbons in the ozonide correlate to the
substituents of the carbonyl
Make sure you know the Ozonolysis mechanism - the tips above are JUST for checking your
mechanism arrows!
Make sure you fill in the scantron correctly! Sometimes the order of the questions is NOT
straight down the page - dont miss the easy points!
The summary sheets from lecture are so helpful, dont ignore them during studying!
alkene
1) O3
2) DMS (dimethyl
sulfide) (CH3-S-CH3)
aldehydes or
ketones
or
Acetic acid (HOAc)
(vinegar) + Zn metal
or dust
or
H+ (any acid)
oxidative
ozonolysis
alkene
oxycope
1) O3
2)H2O2 + H+
heat
or
potassium hydride
(K+H:-) at room temp
aldehydes or
ketones
aldehydes or
ketones
(enol keto)
Mild oxidation
alkyne hydrolysis
2o or 1o alcohol
alkyne
PCC (pryridinium
chlorochromate) (pyr
CrO3 HCl)
2o ketone
1) 9-BBN (9borabicyclononane)
aldehyde (keto)
(anti-markovnikov)
1 aldehyde
or
BH3
or
disaiamylborane
(Sia2B-H)
2) H2O2, -OH, H2O
alkyne hydrolysis
alkyne
H+, H2O
or Hg+2, H3O+
oxidative cleavage
HIO4
or
ketone (keto)
(markovnikov)
aldehydes and
ketones
acid halide
H2 gas, Pd/BaSO4
(cat) w/ quinolone
aldehyde
or
1)LiAlH(OtBu)3
2)H3O+
Gilmans cuprate
acid halide
1) (CH3)2CuLi
ketones
2) H3O+
prep from nitriles
nitrile
1)DIBAL-H
2)H3O+
aldehyde
nitrile
ketone
2) H3O+
Making Alcohols
From alkenes:
Name
Reactants
Type of
Addition
Products
Hydrolysis:
Hydroboration/Oxidation
(1) BH3
(Borane),THF
(Tetrahydrofuran)
(solvent)
(2) H2O2 (hydrogen
peroxide), HO-,
H2O
SYN Addition
AntiMarkovnikov
addition
Markovnikov
Addition
Hydrolysis:
OxyMercuration/Reduction
ANTI Addition
Epoxide Formation &
Opening
Both
enantiomers are
produced
Tertiary (3)
alcohols
Both
enantiomers are
produced
Trans Diol (if
cyclic)
Cis-Dihydroxylation:
Osmium Tetroxide
OR
(1)OsO4 (cat. ~
1%)
(2) NMO (N-methyl
morpholine NOxide
Ozonolysis: Reductive
workup
1). O3
2). NaBH4
10 and 20
alcohols