Chemistry Reference
In-Depth Information
MeO
MeO
Pd(OAc)
2
, py,
n
-Bu
4
NCl, CO
MeO
MeO
I
O
4.93
4.94
Scheme 4.38
O
H
I
(Ph
3
P)
2
PdCl
2
,
MeOH, Et
3
N, CO
O
CO
2
Me
MeO
MeO
4.95
4.96
Scheme 4.39
O
I
PdL
n
I
PdL
n
I
PdL
n
oxidative
addition
CO
insertion
MeO
MeO
MeO
4.97
4.98
4.95
O
O
O
PdL
n
I
PdL
n
I
alkene
insertion
CO
insertion
alkene
insertion
MeO
MeO
4.99
4.100
O
O
O
H
H
H
MeOH
O
O
O
CO
insertion
O
CO
2
Me
PdL
n
I
MeO
MeO
MeO
PdL
n
I
4.101
4.102
4.96
Scheme 4.40
CO
2
Me
PdCl
2
, CuCl
2
,
NaOAc, CO, MeOH
PhO
PhO
4.103
4.104
Scheme 4.41
4.3.2 Other Carbonylation Reactions of Allenes and Alkynes
Terminal alkynes
4.103
may be converted in propiolic esters
4.104
under conditions that look very like
a Wacker oxidation (see Chapter 6, Section 6.1) (Scheme 4.41).
40
The reaction is likely to proceed via
the copper(I) acetylide. This is a mild alternative to the classical method of employing a strong base and
quenching the acetylide anion with a chloroformate.
