Morphinecodeineheroin. Ibuprofen R form non-active side effects S form active anti-inflammatory.
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Transcript of Morphinecodeineheroin. Ibuprofen R form non-active side effects S form active anti-inflammatory.
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O
HO
HO
N
HH
CH3
O
H3CO
HO
N
HH
CH3
O
H3CCO
H3CCO
N
HH
CH3
O
O
morphine codeine heroin
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Ibuprofen
OH
O
H3C H
OH
O
H CH3
R formnon-activeside effects
S formactive
anti-inflammatory
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R.B. Woodward (1917-1979)
•1965 Nobel Prize in Chemistry•“outstanding achievements in the art of organic synthesis
•Also made VERY important observations in the development of the Woodward-Hoffman rules of ring closure•1st step in the application of quantum mechanics to organic molecules•1981 Nobel Prize in Chemistry (Roald Hoffmann)
•1st modern synthetic organic chemist•Probably greatest organic chemist
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R.B. Woodward (Early Career)
Ferrocene
Fe
Penicillin V
N
S
O
NH
H
H
COOH
CH3
CH3
PhOH2C
O
Tetracycline
OH O OH O
CONH2
OH
N(CH3)2H
H3C OHH
OH
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R.B. Woodward (Later Career)
Quininewith von E. Doering, 1944
N
OCH3
NHO
H
HO
CH3 H
CH3
H H
Cholesterol1951
Reserpine1956
NH
NH3CO
H
H
H
OCH3H3COOC
O
O OCH3
OCH3
OCH3
Cephalosporin C1966
NS
N
O
O
CH3O
NH3
OOC
OH
HOOC
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R.B. Woodward
Vitamin B12with Eschenmoser, 1972
N
N N
N
CH3
CH3
Co
H3CH3C
CH3
CH2CH2CONH2
CH3H
H
CH3 H
CH3
H
CONH2
H2NOC
H2NOC
H2NOC
NH
O
OP
O
O
O
O
OH
N
N CH3
CH3
HO
CONH2
H
H3C
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K.C. Nicolaou
•Penn (1977-1989)•Scripps Research Institute and UC-San Diego (1989-present)•Modern day R.B. Woodward
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K.C. NicolaouTaxol
OH
O
HO
AcO
AcOH
OBz
O
O
NH
Ph
O OPh
OH
11 stereocenters => 211 = 2048 stereoisomers2 rings & 1 bicyclic ring
• Isolated in 1967 from bark of Pacific yew tree• Lung, ovarian, breast, head and neck cancer
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K.C. NicolaouBrevotoxin B
23 stereocenters => 223 = 8,400,000 stereoisomers11 trans-fused rings83 steps, 12 years91% yield for each step but 0.043% total yield
O
O
O
O
O
O
O
O
MeH Me H
H
Me Me H
MeH H H
HH H
OO
O O
H
H
H
HO
Me
H
H
HO
Me
• Neurotoxin that binds to voltage-gated sodium channels in nerve cells
• Naturally found in Karenia brevis which are marine organisms typically found in fish
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K.C. NicolaouMaitotoxin
94 stereocenters => 294 = 1.98 x 1028 stereoisomers31 trans-fused rings
• Neurotoxin that binds to calcium channels• Naturally produced by Gambierdiscus
toxicus which are marine organisms typically found in fish
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Atomic Orbitals
n l Orbital Name
1 0 1s
2 0 2s
2 1 2p
3 0 3s
3 1 3p
3 2 3d
n l ml Orbital Name
1 0 0 1s
2 0 0 2s
2 1
-1
2p0
+1
3 0 0 3s
3 1
-1
3p0
+1
3 2
-2
3d
-1
0
1
2
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Linus Pauling (1901-1994)
• “The Nature of the Chemical Bond”• Protein Structure• Antibody Structure and Process• Molecular cause of Sickle-cell anemia• Electronegativity• Resonance• Vitamin C and the Common Cold
• Probably greatest chemist of the 20th century
• Only person too win 2 unshared Nobel Prizes and only person to win 2 unrelated Nobel Prizes• 1954 – Chemistry• 1962 - Peace
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The Periodic Table and Electronegativity
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Common Bonding Situations
Hydrogen 1 bond O HH
Carbon 4 bonds (neutral and 8 electrons)
C C
H
H
H
H
H
H4 single bonds
C C
H
H
H
Hdouble bond
C CH H
triple bond
Reactive Carbon Species
CH
H
H
+
carbocation
CH
H
Hradical
CH
H
H
_
carbanion
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Nitrogen 3 bonds and one unshared pair of electrons
C N
H
H
H H
H C N
H
H
H
C NH
Other relatively stable species
NH
H
H
H
+
4 bonds + charge
NH
H2 bonds2 pairs
- charge
_
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Oxygen 2 bonds and 2 unshared electron pairs
C O
H
H
H
H C O
H
H
Other relatively stable species
OH
H
H+
3 bonds1 pair+charge
H O
_
1 bond3 pairs
- charge
hydronium ion
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Halogens 1 bond and 3 unshared electron pairs
C BrH
H
H
also 4 unshared pairs and negative charge
Cl_
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Table 2-6a, p. 51
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Table 2-6b, p. 51
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These are sigma () MOs: symmetrical about the internuclear axis
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OO
C
O
C
O
O
C
O
Energy