Biomedical Engineering Reference
In-Depth Information
CuI, CsOAc
DMSO, 80°C
(85%)
SMe
OH
O
OMe
HN
CuI, CsOAc
DMSO, rt
(77%)
CuI, CsOAc
DMSO, 90°C
(80%)
H
N
N
O
MeO
OH
O
H
O
CuI, CsOAc
DMSO, rt
(100%)
CuI, CsOAc
DMSO, 60°C
(83%)
SCHEME 3.31
(
þ
)-Yatakemycin synthesis by Fukuyama and coworkers.
far. The same strategy had been applied to several natural products as exemplified in
Scheme 3.32. Indeed, the combination of CuI and
N,N
0
-dimethylethylenediamine
(Buchwald's catalytic system) affords the desired cross-coupling products in high
yields and allowed the syntheses of abyssenine A [79], mucronine E [80], paliurine
F [81], and ziziphines N and Q [82]. On the basis of similar key catalytic steps,
Panek and coworkers reported the total synthesis of the reblastatin, a cell cycle
inhibitor [83].
O
O
NH
2
X
NH
MeO
R
I
MeO
R
MeO
R
CuI,
L11
Cs
2
CO
3
THF, 60°C
TMSOTf
2,6-lutidine
CH
2
Cl
2
Boc
Boc
N
N
MeHN
Me
NH
O
O
O
H
N
O
Me
Me
NH
NH
NH
NH
O
O
−
20°C-0°C
NH
2
Me
Me
NH
Me
NH
Me
O
Me
Me
Me
Me
O
O
Me
Me
Me
82
83
R = H (82%)
84
R = OMe (84%)
Abyssenine A: R = H
Mucronine E: R = OMe
CuI,
L11
Cs
2
CO
3
PhMe, 60°C
(70%)
CuI,
L11
, K
2
CO
3
PhMe, 100°C
(80%)
OMe
OMe
OH
O
O
O
MeO
O
O
O
O
NH
NH
N
N
N
HN
H
CuI,
L11
Cs
2
CO
3
PhMe, 60°C
(82%)
Me
O
O
Me
R
Me
Me
Me
OH
MeO
O
Me
O
O
HN
HN
Me
NH
2
MeO
Me
Me
Me
2
N
Me
2
N
Me
Me
Me
Paliurine F
Evano and coworkers (2007)
Ziziphine N: R = CH
2
CH(Me)
2
Ziziphine Q: R = CH(Me)
2
Evano and coworkers (2009)
Reblastatin
Panek and coworkers (2005)
SCHEME 3.32
Examples of enamide formation under Cu-catalyzed macrocylization.
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