Chemistry Reference
In-Depth Information
TABLE 8B.10. Allylic Alkylations at 2 - Substituted 2 - Cycloalkenyl Carbonates
R
R
OCO
2
Me
CH(CO
2
Me)
2
CH
2
(CO
2
Me)
2
Pd(dba)
2
,
L*
,BSA,
LiOAc, solvent
()
n-4
()
n-4
Ph
N
N
H
Ph
P
P
O
N
Ph
DIAPHOX
(
L18
)
9-PBN
(
L17)
Time
(h)
Yield
(%)
e e
(%)
Entry
n
R
Ligand
Solvent
Reference
1
6
CH
3
L17
12
ClCH
2
CH
2
Cl
95
51
101
2
6
P h
L17
2
ClCH
2
CH
2
Cl
97
95
101
3
6
C
CSiMe
3
L17
3
ClCH
2
CH
2
Cl
97
90
101
4
6
2 - Furyl
L17
4
ClCH
2
CH
2
Cl
96
54
101
5
5
CH
3
L17
12
THF
97
50
101
6
5
P h
L17
4
ClCH
2
CH
2
Cl
96
83
101
7
a
6
P h
Ph - DIAPHOX
(
L18
)
4
CH
3
CN
94
80
102
8
a
,
b
6
P h
Ph DIAPHOX
(
L18
)
4
CH
3
CN
54
91
102
a
[Pd( π - C
3
H
5
)Cl]
2
was used as Pd source.
b
CH
2
(CO
2
Bn)
2
was used as pronucleophile.
[Pd
II
]
OCOR
Nu
Nu-H
Nu-H/Cs
2
CO
3
ROCO
OCOR
ROCO
OCOR
[Pd
2
(dba)
3
]CHCl
3
,
(
R
,
R
)-
DPPBA-1
,
THF
ROCO
OCOR
OCOR
OCOR
OCOR
(
rac
)
R = CH
2
CCl
3
Nu-H
Yield (%)
ee (%)
HO
O
OH
81
88
PhO
2
S
N
ONa
O
OH
OH
OO
95
96
(-)-Cyclophellitol
O
O
Scheme 8B.19.
Conduritol B as substrate for the allylic alkylation.
