Topics in Current Chemistry (2020) 378:16
1 3
OPfp
O
OPfp
O
H
[B]
X
Pd 2 dba 3 (2.5 mol%)
BINAP (10 mol%)
(S)-BTM (20 mol%)
i Pr 2 NEt (1.3 equiv.)
THF, rt
20 Examples, E:Z ratio >20:1
[B]
OPfp
O
H
64%
89% ee
BPin
MeO
OPfp
O
H
BPin
74%
86% ee
Br
OPfp
O
H
BPin
OPfp
O
H
BMIDA
50%
88% ee
Me
Me
Me
65%
70% ee
Pd II
[B]
L
L
Pd II
L
L
[B]
Ar
OPfp
O
H
[B]
Ar
OPfp
O
H
[B]
Ligand-centered control over alkene stereochemistry via syn- and anti- cataionic π(allyl)Pd intermediates:
Selected Examples:
X = OMs, OCO 2
t Bu
syn-complex
anti-complex
gives
E-alkene
(major)
gives
Z-alkene
(minor)
H
H
Scheme 20 Allylation using boron-substituted electrophiles
Scheme 21 π-Extended electrophiles for benzylation
Reprinted from the journal
118
1 3
OPfp
O
OPfp
O
H
[B]
X
Pd 2 dba 3 (2.5 mol%)
BINAP (10 mol%)
(S)-BTM (20 mol%)
i Pr 2 NEt (1.3 equiv.)
THF, rt
20 Examples, E:Z ratio >20:1
[B]
OPfp
O
H
64%
89% ee
BPin
MeO
OPfp
O
H
BPin
74%
86% ee
Br
OPfp
O
H
BPin
OPfp
O
H
BMIDA
50%
88% ee
Me
Me
Me
65%
70% ee
Pd II
[B]
L
L
Pd II
L
L
[B]
Ar
OPfp
O
H
[B]
Ar
OPfp
O
H
[B]
Ligand-centered control over alkene stereochemistry via syn- and anti- cataionic π(allyl)Pd intermediates:
Selected Examples:
X = OMs, OCO 2
t Bu
syn-complex
anti-complex
gives
E-alkene
(major)
gives
Z-alkene
(minor)
H
H
Scheme 20 Allylation using boron-substituted electrophiles
Scheme 21 π-Extended electrophiles for benzylation
Reprinted from the journal
118