coupling rxns
TRANSCRIPT
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1972
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,
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1977
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(.. , , ).
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8/12/2019 Coupling Rxns
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L Pd
L
L
Pd
LL
L
-dbadba
I
oxidative
addition
reductive
elimination
Fe
L Pd
L
Fe
I Pd
L
L
L
Pd
L
I ZnCl
transmetalation
Fe
ZnCl
Fe
isomerization
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8/12/2019 Coupling Rxns
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, .
, ,
.
,
.
.
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.
.
() .
()
.
, .
..
, .
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Ph3P Pd
PPh3
Ph3P
Pd
PPh3
PPh3
PPh3
-2PPh32PPh3
I Pd
PPh3
I
oxidative
addition
isomerization &
reductiveelimination
Ar'
Pd
PPh3
Ph3P
Ph3
P
KI
transmetalation
KOAc
AcO Pd
Ph3P
PPh3
B
O
O
AcO
PdPh3P
PPh3
B
O
O
B
O
O
B
O
O
O
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8/12/2019 Coupling Rxns
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.
.
( ), ,
.
, .. ,
.
,
.
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, ,
, .
. ( ) .
, .
,
.
( ),
.
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Ph3P Pd
PPh3
Ph3P
Pd
PPh3
PPh3
PPh3
-2PPh32PPh3
I
oxidative
additionisomerization &
reductive
elimination
Ar'
I Pd
Ph3P
PPh3
KI
transmetalation KOAc
AcO Pd
Ph3P
PPh3
Ar'
B
O
O Ar
'B O
O
OAc
AcO
B O
O
OAc
Ar'
Pd
Ph3P
3
KOAc
K+
K+
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.
.
1975
.
.
, () , .
, ,
.
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Ph3P Pd
PPh3
Ph3P
Pd
PPh3
PPh3
PPh3
-2PPh32PPh3
PPh3
I
oxidative
addition
reductive
elimination
PPh3
R
I Pd
Ph3P
transmetalation
Pd
Ph3P
PPh3
Ph3P Pd
Cu R
CuI
H RNEt3 +
HNEt3 I
R
R
isomerization
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.
.
,
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, .. ,
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.
1,2 . 1,2
.
, .
,
.
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Ph3P Pd
PPh3
Ph3P
Pd
PPh3
PPh3
PPh3
-2PPh32PPh3
Br Pd
Ph3P
PPh3
Br
oxidativeaddition
reductive
elimination
Pd
Ph3P
PPh3BrH
OO
NEt3
HNEt3Br
1,2-insertionPd
Ph3P
PPh3
Brelimination
O
O
O
O
Br Pd
Ph3P PPh3
O
O
H
Pd
Ph3P
PPh3Br
O
O
H
association
dissociation
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.
( ) .
.
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