Chem 332 Reactions Exam 1 :

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

12. BH3 and THF chemo selective for Carboxylic acids

13. Great Nucleophile reactions 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

Chemo selective Reactions:

1. Wittig aldehydes/ ketones
2. Acetal/Ketal formation aldehydes/ketones
3. Cuprates acid halides
with cadmium as well
4.. Rosenmunds acid halides
LiAlH(Ot-Bu)3 selective for acid halides ONLY
DIBAL with acid Halides dont go to alcohol
Name Reactions:
1. Diels-Alder
2. Grignard - adding a carbon!
3. Jones
4. Fieser
5. Tollens
6. Rosenmunds
7. Gilmans Cuprate
9. Arthur-Cope / Oxycope
10.Wittig reaction
-Know the mechanism and intermediates
11.Williamson Ether synthesis
12. Claisen Rearrangement
13.
14.

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!

Making Aldehydes and Ketones

normal ozonolysis

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

1,5 isolated diene

with alcohol

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

cis alcohol (1,2

viscinal)

HIO4
or

ketone (keto)
(markovnikov)

aldehydes and
ketones

NaIO4, H2O, THF

Rosenmunds
hydrogenation

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

prep from nitriles

1) R:- +Mg (grignard)

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

Primary (1) and

Secondary (2)
alcohols

(1) Hg(OAc)2, H2O

(2) NaBH4 (sodium
borohydride)

Markovnikov
Addition

Hydrolysis:
OxyMercuration/Reduction

ANTI Addition
Epoxide Formation &
Opening

(1) m-CPBA (or

any other peroxide)
SYN Addition
(2) H3O+
ANTI Addition
OR
(1) m-CPBA (or
any other peroxide)
SYN Addition
(2) (a) HO- (b) H+
ANTI Addition

Both
enantiomers are
produced

Tertiary (3)
alcohols
Both
enantiomers are
produced
Trans Diol (if
cyclic)

Cis-Dihydroxylation:
Osmium Tetroxide

(1) OsO4 (Osmium

tetroxide)
(2) NaHSO3 (aq)

Cis Diol (if

cyclic)

OR
(1)OsO4 (cat. ~
1%)
(2) NMO (N-methyl
morpholine NOxide
Ozonolysis: Reductive
workup

1). O3
2). NaBH4

10 and 20
alcohols