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Advanced Organic Reactions 2000 - Warren

Advanced Organic Reactions 2000 - Warren

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Published by: shiv57 on Apr 02, 2010
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01/03/2013

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SELECTIVITY 1
SELECTIVITY
Science
 
1983
,
219
, 245
Chemoselectivity
preferential reactivity of one functional group (FG) over another- Chemoselective reduction of C=C over C=O:
O
H
2
,Pd/C
O
- Chemoselective reduction of C=O over C=C:
O
NaBH
4
OH O
+
O
NaBH
4
, CeCl
3
OH
only
- Epoxidation:
OH OH OH
+
MCPBA
O O
(2 : 1)
OHOHO
VO(acac)
2
,tBuOOHexclusively
Regioselectivity
- Hydration of C=C:
RROHROH
1) Hg(OAc)
2
, H
2
O2) NaBH
4
1) B
2
H
6
2) H
2
O
2
, NaOH
- Friedel-Crafts Reaction:
RCOCl,AlCl
3
+
RORO
RCOCl,AlCl
3
ROSiMe
3
 
SELECTIVITY 2- Diels-Alder Reaction:
RO
+
RR O
+
O
majorminor
O
+
O
+
O
majorminor
RRR
OOOHOAc
+
OOOHOAcOOOHSPh
+
OOOHSPhOAcOAc
Raney Ni, H
2
OOOHOAc
Change in mechanism:
RRR
PhSH, H
+
SPhSPh
PhSH, (PhCO
2
)
2
Stereochemistry:Relative stereochemistry: Stereochemical relationship between two or more stereogenic centerswithin a molecule
HOHHOHHH
enantiomerssame relative stereochemistrycholesterol
syn: on the same side ( cis)anti: on the opposite side (trans)- differences in relative stereochemistry lead to diastereomers.Diastereomers= stereoisomers which are not mirror images; usually have different physicalproperties
 
SELECTIVITY 3Absolute Stereochemistry: Absolute stereochemical assignment of each stereocenter (R vs S)Cahn-Ingold-Prelog Convention (sequence rules)- differences in absolute stereochemistry (of all stereocenters within the molecule) leads toenantiomers.- Reactions can "create" stereocenters
PhHO
MeMgBr
PhHHOCH
3
PhHO
MeMgBrMeMgBr
PhHH
3
COHPhHHOCH
3
enantiomers(racemic product)
Diastereomeric transition states- not necessarily equal in energy
Ph HHO CH
3
ONMeMeZnZnCH
3
H
3
CCH
3
OPhHONMeMeZnZnCH
3
H
3
CCH
3
OHPhH PhHO CH
3
Diastereoselectivity
PhCHO
CH
3
MgBr
PhCH
3
HOHPhCH
3
HOH
+
synantiDiastereomers
Cram Model (Cram's Rule): empirical
PhOH
3
C H
CH
3
MgBrCH
3
MgBrfavored
ROLSMLOMSR
Nu
H

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