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Corey: B-Sides
iPr
OTf
CsF, PhNTf2
nBu
Me
NNMe2
nBu
SMe
THF:H2O, 1h,
100%
NOH
O
tBu
ii. Cr(OAc)2,
THF:H2O,
65 C, 16h, 88%
Br
Ph
Br
C6H6, TsOH
87%
Br
Br i. BzCl, py
O
3
OTBS
CHO
3
OH
OTMS
TMSCl, LOBA
nBu
Alloc-O
nBu
OSO2F
Me
S
O
S
OtBu
OC6H4-p-OMe
5:1 (-100 C)
tBu
Tr
N
Li
TL, 2000, 41, 2515
TrN
Li
tBu
Me
R
MeOH, rt,
2h, 73%
Ph
i. TMSCl, LiBr
ii. Pd(OAc)2, BQ
91% ee
Me
R R
OTMS
HO
Ni(CO)4, 92%
iPr
Me
S
Me
n-C5H11
97:3
Me
OH
DIBAL, 23 C
iPr
RCO2H
TL, 1977, 18, 2081
95%
OBz
ii. Zn-Ag
THF, 84%
Me
JOC, 1973, 28, 3224
For 5-methylene-1,3-dioxanes: TL, 1975, 16, 3775
ii. KSCN
n-C5H11
OH
HO
i. Hg(OAc)2, MeOH
O
OH
i. Ac2O
OH
ii. pH 2 brine
93%
SMe
Cu(OAc)2
tBu
iPr
i. RhCl(PPh3)3
EtOH(aq), !
DME, 23 C, 78%
Me
Tim Newhouse
R R
MeOH, rt,
18h, 87%
MeS
S
OMe
R R
MeO
OMe
R R
TL, 1975, 16, 3267
E. J. Corey: B-Sides
Tim Newhouse
OH
OTBS
OTBS
OTBS
Me
Me
Me
OTBS
OH
IBX, DMSO
Me
H
HO
tBu
tBu
DCM, rt, 1 atm:
24h: 100% SM - 15h : 94% alcohol - 93% SM, 4% alcohol - 24h: 100% SM
tBu
tBu
H
HO
O
tBu
92% ee
MeOH, rt
tBu
1! O
g 2
KO2 + H2O
C(NO2)4, DMSO
i. PDC
ii. Ac2O, tBuOH
NO2
RN3
ii. O3
tBu
NH2
OH
R2CO
oxalic acid
H2O
tBu
OH
JACS, 1969, 91, 1429
tBu
RCO2tBu
R
tBu
HN
NCHR
R2CHNH2
H
N
SnMe3
H
N
H H
pKa = 4.7 (EtOH/H2O)
i. TiCl4, 60%
Me
Br
Br
RNO2
Ni(CO)4, CO
E
NMP, 50 C
CO2Me
Me
E. J. Corey: B-Sides
tBu
tBu
OMe
CO2H
CO2 (1 atm)
tBu
i. Tl2SO4, KOH
rt, 16 h, 89%
Me
Tim Newhouse
ii. Cl
OMe
-20 C, 5h, 1 mol
tBu
+ TlCl
JACS, 1971, 93, 1489
NBA
SnCl4 or BF3Et2O
OH
EtOCHO, NaH
NHAc
Br
H3C
OOH
Me
Me
Me
Me
pTsCl, py
5-10%
i. py-SO3, 0 C
OH
Ph
O
i. PhSCH2- Cu+, 76%
Br
i.
P Cl
, py
RI +
ii. I2
ArO2SN
TsCl, py
NSO2Ar
O
I
O
RNC
JACS, 1958, 80, 2903
O2N
HO
2 days
50:1 dr, 100%
97% ee
Ph
Ph
Method development:
Applications:
Me O
4 C
Ph
Ph
B
Br
O
Ph
P
JOC, 1967, 32, 4160
RNHCHO
Ph
2NEt
-78 C
O
O
ROH
iPr
Ph
*
OBR2
Me O
NO2
base, 2h
0 C ! rt, 62%
O
OHC
E. J. Corey: B-Sides
i.
C5H11
Ph
Ph
A=
H OH
Ph
A, -78 C, 2h
DCM
NSO2Tol
TolO2SN
C5H11
B
H OMOM 80%, dr = 25:1
H OMOM
allyl
opposite ent: dr = 39:1
up to 99% ee for allylations
JACS, 1989, 111, 5495
SnBu3
JACS, 1981, 103, 4618
H OH
H OH
or
or
R-CHO
R
R
S
nBuLi
SnPh
Ph
Li - en
HMPA:THF,
-20 C, 12h
TBSO
S
S
S
BF4
0-25 C, 96%
CHO
96%
S
OH
200 C, 4h
97%
94%
Me
Me
H
HO
OH
BnO
OBn
O
Et2Zn
Zn
Ar Et
CO2Me
Me
OH
Zn/TMSCl
2,6-lutidine, THF
77%
CO2Me
C6H5
Et
OH
OH
Me
Me N
N
Me
Li
Me
Me
OH
OH
0 C, 30 min
93%
NaCNBH3, 91%
NH2
HCl, NaNO2,
THF, 0 C;
PhCHO
i. PCC
Mg(Hg)-TiCl4
OBn
Me
HgCl2, CaCO3
Tim Newhouse
HO
Et
90% ee
H
TL, 1987, 28, 5233
Alternate catalyst and mechanistic studies: JOC, 1990, 55, 784
Ph
C3H7-CO2Me
nC H -Br
4 9
Mg, ClTi(OiPr)
rt, 79%
C2H5
HO
3
C3H7
single diastereomer
E. J. Corey: B-Sides
Br
CO2Et
Me
Me
O
CH2
O
S
OEt
OEt
i. THF, !
CO2Me
SOMe
Me
LiCuMe2
0 C, 2.5h, 81%
sBuLi
-78 - 50 C
CHO
JACS, 1970, 92, 5522
Me
Me
Br
0 C, 68%
tBu
0 C, 85%
CuCH2CN
Pd(OAc)2, TBHP
K2CO3
Pd/C, TBHP
K2CO3
tBu
Tim Newhouse
CN
OOtBu
Me
Me
Me
Me
TL, 1972, 13, 487
OH
Me
CH2I2, Zn-Cu
NHTrisyl
CHO
350 C
Me
90%
H
Me
Me
JACS, 1970, 92, 6636
O
O
TMS
O
O(nBu4N)
I
OBn
82%
O Ph3P Me
tBuLi,
i.
-40 C
ii. 0 C - rt, 20 h
54%
OH
PhCHO
O
PPh3
TsO
Br
O(nBu4N)
OBn
TMS
Me
64%
Me
O
JACS, 1982, 104, 4725
OTBS
vinyl-Li, -78 C
Ph
TBS
then I2, 2h
74%
2
JACS, 2002, 124, 11290
E. J. Corey: B-Sides
BF3K
Me
O
Ph
EtLi, CuI
OH
Me
90%, 92% ee
N
Me
NMe2
Me
[Rh(cod)2]BF4, BINAP
PhMe, Et3N, rt, 3 days
87%, >98% ee
Tim Newhouse
O
Ni(CO)4, BuLi
-50 C, 12h, 64%
ArOCH2Cl + LiSnBrCl2
O
Bu
"
O
i.
Bu3Sn
ArOCH2SnBrCl2
i. sBuLi / KOtBu
ii. CuBr
OtBu
ArOCH2Li + Bu4Sn
O
tBuOMe
4 eq BuLi
"
CuCCPh
Li
THF
THPO O
THPO
CuLi
O
O
37%
CO2Me
CO2Me
JACS, 1972, 94, 4014
"
Ar2
P
NiCl2
P
Ar2
CHO
MeS
iBu
Ph
2Al
PhMe, -45 C,
74%, 85% ee
OH
OMe
OH
SMe
SMe
Ar = m-terphenyl
Me Me
"
82%
SMe
CHO
Ph
OMe
Me
Si
Me
MeO
Me
Si
Me
OMe
Me
MeLi, THF:HMPA
Si
-50 C, 5h
Me
Li