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11 Chemoselectivity (Part 1+2 Redox)
11 Chemoselectivity (Part 1+2 Redox)
11 Chemoselectivity (Part 1+2 Redox)
Reference:
• Reduction
• Oxidation
Oxidation
• Protection
Reduction
H H O O
H OH
R H R H R H R OH
H O O
NH 2
R H R R' R X
R = OR', NR' 2, Cl,...
Part 1: Reduction
1.1 Reduction with metal hydrides
1.2 Catalytic hydrogenation
1.3 Dissolving metal reduction
1.4 Removal of functional group
1.2.5 Hydrogenolysis
Stereoselectivity:
syn-addition
Catalyst (Pd) is
poisoned by Pb
• Arenes (aromatic ring, most common phenyl ring) can also be reduced
• Various temperature, pressure and catalyst (usually by trial-and-error)
is used for different selectivity
BaSO4 has low surface area, hence lower the activity of Pd catalyst. Pd can be
further poisoned by quinoline to reduce its activity to avoid over-reduction.
Compare with
the DIBAL
reduction of
ester to afford
aldehyde:
[Nitrile (C≡N)
can also be
reduced to
amine.]
Reduction of RNO2:
Reduction also by Sn/HCl:
Relative
rather than
black-and-
white
Many cases
trial-and-error
Various T, p,
cat.
unconjugated
diene product
kinetic
control
Neutral
condition
1.dithiol, BF3
2.RaNi (H2)
RaNi: Raney nickel – an reagent (stoichiometric amount) instead of a catalyst
Ni-Al alloy + NaOH à RaNi (H2 absorbed on Ni surface)
• Wolff-Kishner reduction (via elimination of N2 from hydrazone)
Basic condition
1.NH2NH2
2.OH-
• Clemmensen reduction
Acidic condition
1.Zn
2.Concentrated HCl
CM2121 Organic Chemistry 24
Part 2. Oxidation
Part 2: Oxidation
2.1 “Complete” oxidation for carboxylic acid/ketone
2.2 Partial oxidation for aldehyde
2.3 Oxidation of aldehyde to carboxylic acid
2.4 Other types of oxidation (CM1121 Chapter 19)
Very often,
CH2Cl2 is
the solvent
regeneration
of oxidizer
gaseous by-products
b.p. of Me2S: 38 oC
(but very smelly L)
CM2121 Organic Chemistry 28
2.3 Oxidation of Aldehydes to Carboxylic Acids
Pinnick reaction
Sodium chlorite (NaClO2): aldehydesàcarboxylic acid
[very mild condition, selective and also inexpensive]
Of course, strong oxidizing reagent (e.g. KMnO4 and K2Cr2O7) also oxidizes
aldehyde, but at a risk of unwanted side-reactions.
§ Oxidative cleavage
Alkene is oxidized.
Mechanism is by pericyclic
reactions (beyond CM2121
syllabus)