alkene problem bank part b answers...1) n-buli b pd(pph3)4 licl 2) (n-bu)3sncl sn(n-buli)3 ch2i2 pph...
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AlkeneProblemBankPartB:SuggestedAnswers
Problem8
Problem34
O
OS
SMe heatMgBr1) 2) CS2
3) MeI
Br MgBrMg°
A
A
CO2MeMeO2C CO2Me
CO2Me
HO
OH1) H2, Pd/C2) LiAlH4
Na°/NH3
EtOH
Problem37
Problem48
O OHt-BuLi
NO2
O2N SCl
Et3N
BrBr
OH OTHPOHOTs
HO1) EtCu•MgBr2
2) H3O+
Br
PBr3
HBrhυ
EtMgBrCuBr
BrNi(CO)4
Ni
A
Br
2
NiA
Br
2
BrBr
Problem52
Problem70
OH
O
O1) NaH
2) Br
OHheat 1) MeCu
2) PhI
MeLiCuI
O
O O1) LiN(SiMe3)22) PhSeSePh
3) H2O2
OHArSeCl
Et3Ni-Bu2AlH
Problem86
Problem136
H
OI
Ph3P CHI
THF/HMPA
A
O OTf1) BrMgN(i-Pr)2
2) Tf2NPh
excess
1) n-BuLi
B
Pd(PPh3)4LiCl
2) (n-Bu)3SnClSn(n-BuLi)3
CH2I2PPh3
Ph3P CH2II
Ph3P CHI
A
LIN(SiMe3)2
OTf
B
CH3
CH3BrCH3
Br
CH3
MgBrCH3
Mg°
5 mol% catalyst
Fe
PPh2OMe
H CH3NiCl2+catalyst
CH3
CH3
enantiomer shown
Problem150
Problem164
OMe
O
O
OH
O
OMe
OMeOH
TsOH
1)
HB
OTf
OTf
A
Pd(PPh3)4K2PO4
1) i-Pr2NMgBr
2) Tf2NPh
i-Pr2NH1) n-BuLi2) MgBr2
A
OMe
O
O O1) 2 9-BBN
2) BrO
2
Pd(PPh3)4 , K2CO3
O O
Problem165
Problem168
Br1) 2 Li°
2) 1/2 CuI
O
3)OTf
4) Tf2O
MeO Cu(CN)Li22
B
MeO
MeO Cu(CN)Li22B
MeO Br1) n-BuLi
2) 1/2 CuCN
MeO
1) MeCu(SMe2)MgBr2
2) iodineI
1) i-Bu2AlH
2) iodineI
A
1) Mg°I
ANiCl2, 2 PPh3
MeMgBrCuBr2•SMe2
Problem169
Problem279
O
CO2MeMeO2C
NHN S
OOHNH2NHSO2Trisyl 1) 2 n-BuLi
2) BrCH2CH2BrBr
1) n-BuLi
2) 1/2 CuI3) heat
OHHO
LiAlH4CO2MeMeO2C
OHHO
ClOH
OH
CCl3
CHO
CrCl2Cl3C OH
Cl3C H
OPCC
AlCl3
ClOH
Problem402
Problem404
O1) LiN(i-Pr)2
2) Tf2NPh
OTf
Li2CuCl4
MgBr
cat
KF3B1) HBBr2•SMe2
2) H2O3) KHF2, H2O
OO
BF3KO O
O OTf1) LiN(i-Pr)2
2) Tf2NPh
A
OTf
A
cat PdCl2(dppf)Cs2CO3
O
HO Ph3P1) PBr3
2) PPh3
Br OH
n-BuLi
Br
9-BBN1 equiv
Br
A
PdCl2(dppf)2K2CO3
Br-9-BBN HOAc
A
Problem408
Problem409
O Oiodine
pyridine
IOTBS
INaBH4 t-BuMe2SiClimidazole
O
O
O
Br
Br2
PPh3
O
Br
Pd(PPh3)4
A
A
1) 2 t-BuLi
2) ZnBr2
OO
OO
EtO EtO
n-Bu3Sn1) n-BuLi
2) n-Bu3SnCl EtOBr
PdCl2(CH3CN)2
OH
BF3•OEt2
EtO
H
O
EtO
Ph3P
Br1) PPh3
2) n-BuLi
EtO
Problem411
Problem414
HO
H
OBr
Br BrPPh3
CBr4
BF3K
Pd(PPh3)4Cs2CO3
1) n-BuLi
2) DMF
HO
OH
Br
OTBS
Br
t-BuMe2SiClimidazole
BrBr
Br
Br
1) n-BuLi2) 1/2 CuI 0.5 equiv OTBSTBSO
OTfTfO
1) n-Bu4NF
2) Tf2O, pyridine
Me3SnSnMe3
Pd(PPh3)4LiCl
CHBr3
NaOHA
A
Problem415
HO HO
SiMe31) 2 n-BuLi2) 2 Me3SiCl3) H3O+
Br
SiMe3PBr3
BrMg OTHPBr OH
BrMg OTHP
OTHP
SiMe3
A
H
SiMe3
O
1) H3O+
2) PCC
SiMe3
O
1) MeMgBr2) H3O+
SiMe3
OTf
1) LiN(i-Pr)2
2) Tf2NPh
n-Bu4NF
OTf
1) 9-BBN2) Pd(PPh3)4
K3PO4
A
O
HOTs
Li2CuCl4
Mg°
3) PCC
Problem416
O OIiodine
pyridine
OOTHP
BBN OTHP
BBN OTHPA
A
PdCl2(dppf)2Cs2CO3
CuLi2B
CuLi2B
OOTHP
OOHH3O+
OH OTHPO
HOTs9-BBN
SiMe3
1) EtMgBr2) Me3SiCl
SiMe31) Cy2BH
2) HOAc
Br
1) Br2
2) NaOMe
1) n-BuLi
2) 1/2 CuI
OOH
Problem426
Problem433
HO TfO
1) LiN(i-Pr)2
2) Tf2OO
PCC (excess)
Pd(OAc)2
Br
Pd(OAc)2PPh3, Et3N
I
Br Br
HO
OH
Pd(OAc)2
[bmim] [BF4]dppp
Br
THPO
OHOTs
Mg°O
OMe
OHHO MeHO
OHHO MeHO
Problem434
Problem436
O
H
O
H
EtO O
Br Br
Br Br
BO O
B BO
OO
O
[Ir(OMe)(cod)]2dtbpy
Br Br
EtO O
OOEt
Pd(OAc)2O2, Na2CO3
Pd(OAc)2P(o-tol)3
OH
3 equiv
O
H
O
H
EtO O
(CF3SO2)2Opyridine
Br OH Br OTf OTfHOMg°
OH
N
N OTf
N Br
NH2
[Pd(allyl)Cl]2Cy2NMe
[t-Bu3PH] [BF4]
DIADNaOAc
N N O
OO
ODIAD
N
N OTf
Problem437
Problem449
OH
OHOBrO
HOLi°, NH3 BrBr OH
Pd(OAc)2P(o-tol)3
Et3N
MeI
acetoneK2CO3
O
LiAlH4
OH
HO HO1) Br2
2) NaNH2
HO B(OH)2
HO
bombykolTetrahedron 1983, 39, 3271
OB
OH1)
2) H2O
Br
BrA
Pd(PPh3)4NaOEt
B(OH)2
OB
OH1)
2) H2O
1) Br2
2) NaOEt
HO
bombykolTetrahedron 1983, 39, 3271
Problem463
Problem466
O
CO2Me
TiCl4Li° OH
HOOsO4
NMOPOCl3pyridine
OOMe
1) LiAlH42) TsCl, pyr3) DBU
N
O
ONMO
N
NDBU
O OTBSLiN(i-Pr)2excessketone
t-BuMe2SiCl
OTBS
CO2EtOEt
O
OTBS
OH
LiAlH4
O
H
HMeSO2Clpyridine
n-Bu4NF
O
H
H