Sample reactions
intermediate structure
Methyl Cyanoacetate
Cyclohexane, t-BuOH
RT, 48 h, 91%
intermediate structure
intermediate structure
NaSBn
MeOH
RT, 3 h, 77%
intermediate structure
intermediate structure
KOH
EtOH
100 °C, 5 h
"8 mg of strychnine was obtained from a mixture of 7 mg isostrychnine and 65 mg isostrychnine acetates."
intermediate structure
intermediate structure
t-BuOOH, Me3N+Bn HO-
THF
-15 °C, , 91%
intermediate structure
intermediate structure
BnSH, n-BuLi
THF
-50 °C, , 85% (4 steps)
intermediate structure
intermediate structure
MeLi, CuBr, Bz2O2
Et2O
-78 to 0 °C, 45 min, 75%
intermediate structure
intermediate structure intermediate structure
80 °C, 16 h
intermediate structure
intermediate structure
t-BuLi, CuCN, TMSCl
Et2O, Et3N
-78 to -10 °C, 3 h, 93%
intermediate structure
intermediate structure
Ph3COOH, Et3NBn+ i-PrO-
THF
-10 °C, 3 h, 72%
intermediate structure
intermediate structure intermediate structure
MeLi, CuI
THF
0 °C to RT, 45 min, 60%
intermediate structure
intermediate structure
MeLi, CuI, TMSCl
Et2O, Et3N
0 °C to RT, 3.5 h, 80%
intermediate structure
intermediate structure
VinylMgBr, CuI, (CH2NMe2)2, TMSCl
THF, Et3N
90%
intermediate structure
intermediate structure intermediate structure
TMS2NLi
THF, DME
-78 °C, 4.5 h, 71%
intermediate structure
intermediate structure
VinylMgBr, CuI
THF
intermediate structure
intermediate structure intermediate structure
CeCl3
THF
0 °C, , 82%
intermediate structure
intermediate structure
Ethyl vinyl ketone, KOt-Bu, NaOH
t-BuOH, H2O
0 °C to RT, 10 h, 53%
intermediate structure
intermediate structure
VinylCN, Me3N+Bn HO-
PhH, t-BuOH, H2O
50 °C, 45 h
intermediate structure
intermediate structure
MeLi, CuCN, BF3.OEt2
THF
intermediate structure
intermediate structure intermediate structure
n-BuLi
THF
-78 °C to RT, 6 h, 67%
intermediate structure
intermediate structure
MeLi, CuI
Et2O
-78 °C to RT, ON, 97%
intermediate structure
intermediate structure
i-PrCO2Et, i-Pr2NLi
THF
-78 to 0 °C, 2.5 h
intermediate structure
intermediate structure intermediate structure
t-BuLi, CuCN
Et2O
-78 to 0 °C, 2 h, 92%
"99 % yield base on 93 % conversion."
intermediate structure
intermediate structure intermediate structure
i-Pr2NLi
THF
-78 °C to RT, 3 h, 64-85%
intermediate structure
intermediate structure
t-BuOOH, DBU
THF
RT, 72 h, 82%
intermediate structure
intermediate structure
MeLi, CuCN
Et2O
-78 °C, 2 h
intermediate structure
intermediate structure intermediate structure
Li, NH3
THF, t-BuOH
-78 to -5 °C, 75 min
intermediate structure
intermediate structure
KOt-Bu
t-BuOH
intermediate structure
intermediate structure intermediate structure
PhH
Reflux, 22 h, 76%
intermediate structure
intermediate structure intermediate structure
CuBr.Me2S, MeI
HMPA
66%
intermediate structure
intermediate structure
Me2CuLi, AllylCl
THF, HMPA
-78 °C to RT
intermediate structure
intermediate structure
Sc(OTf)3
DCE, H2O
120 °C, 36 h, 73%
intermediate structure
intermediate structure intermediate structure
Et3N
CH2Cl2
RT, 12 h
intermediate structure
intermediate structure
Ph3COOH, n-BuLi
THF
-78 °C, 2 h
intermediate structure
intermediate structure
BnNHMe
RT, 16 h
intermediate structure
intermediate structure
Vinyl2CuMgCl, TMSCl, Et3N
THF
-78 °C to RT
intermediate structure
intermediate structure intermediate structure
K2CO3
THF
Reflux, 4 h, 98%
intermediate structure
intermediate structure
VinylCN, KOt-Bu
THF
0 °C, 20 min, 74%
intermediate structure
intermediate structure
TMSCH2MgCl, CuI, TMSCl, Et3N
THF, HMPA
-78 °C to RT, 2 h
intermediate structure
intermediate structure intermediate structure
TASF
CH2Cl2
-78 °C, 5 min, 79%
intermediate structure
intermediate structure
MeMgBr, CuBr.Me2S, TMSCl
THF, HMPA
-78 °C to RT, 2.5 h
"The starting material was 90:10 er."
intermediate structure
intermediate structure intermediate structure intermediate structure
(n-Bu3PCuI)4, HMPA
THF
-50 °C to RT, 3 h, 60%
intermediate structure
intermediate structure
Me2CuLi
Et2O
-78 °C, 30 min
intermediate structure
intermediate structure
Me2CuLi
Et2O
-78 °C, 30 min
intermediate structure
intermediate structure intermediate structure
CuBr.Me2S
THF, Me2S
-78 to 0 °C, 6 h
intermediate structure
intermediate structure intermediate structure
CuBr.Me2S
THF, Me2S
-78 to 0 °C, , 68%
intermediate structure
intermediate structure
Et3N
Ethylene Glycol
225 °C, 24 h, 8-12%
"The yield was 10-15 % brsm."
intermediate structure
intermediate structure
Me2CuLi
Et2O
-20 °C, 40 min, 96%
intermediate structure
intermediate structure intermediate structure
t-BuLi, (n-Bu3PCuI)4, AcCl
Et2O
-78 to 0 °C, , 84%
intermediate structure
intermediate structure intermediate structure
VinylMgBr, (n-Bu3PCuI)4
THF, HMPA
-45 °C to RT, 3 h, 54%
intermediate structure
intermediate structure intermediate structure
TiCl4
CH2Cl2
-78 °C to RT, 40 min
"R = H, t-Bu."
intermediate structure
intermediate structure
Morpholine, TsOH
PhH
Reflux, , 92%
intermediate structure
intermediate structure
t-BuOOH, NaOH
MeOH, H2O
RT, , 89% (2 steps)
intermediate structure
intermediate structure
Et2AlCN, n-Bu4N+ Ph3SiF2-, Tf2O
PhH
0 °C to RT, 19.5 h, 81%
intermediate structure
intermediate structure
H2O2, NaOH
CH2Cl2, MeOH, H2O
0 °C, 2 h, 75%
"Also isolated was the TES-deprotected product (16 % yield)."
intermediate structure
intermediate structure
VinylMgBr, CuBr.Me2S, TMSCl
THF
-78 °C, 2 h, 92%
intermediate structure
intermediate structure intermediate structure
CuBr.Me2S
THF, Me2S
-78 to 0 °C, 24 h
intermediate structure
intermediate structure
VinylMgBr, CuBr.Me2S
50%
"Also isolate was the C3-epimer (15 % yield)."
intermediate structure
intermediate structure intermediate structure
Mg
Et2O
Reflux, , 13%
"Also isolated was the C3-epimer (40 % yield)."
intermediate structure
intermediate structure intermediate structure
i-Pr2NLi
THF
-100 to -78 °C, , 50%
"For the synthesis of this enone, see : J. Am. Chem. Soc. 1984, 106, 6690."
intermediate structure
intermediate structure
NCCH2CO2Et, K3Fe(CN)6, Et3N
EtOH, H2O
RT, 11 min, 84%
intermediate structure
intermediate structure
NaOCl
Pyr, H2O
0 °C, 60 min, 90%
intermediate structure
intermediate structure
HCl
EtOH, H2O
Reflux, 4 h, 50% (2 steps)
intermediate structure
intermediate structure intermediate structure intermediate structure
ClCH2CO2H
CH2Cl2
0 °C to RT, 3.5 h
intermediate structure
intermediate structure
p-MePhSH
EtOH
-15 °C, 36 h, 70% (2 steps)
intermediate structure
intermediate structure
Methyl propynoate, Et3N
THF
-20 to 0 °C, 3.5 h, 89%
intermediate structure
intermediate structure
TMS2NNa, CuBr.Me2S
NMP
0 to 65 °C, 95 min, 10%
intermediate structure
intermediate structure
NaH
THF
0 °C, 105 min, 98%
intermediate structure
intermediate structure
Dimethyl malonate, KOt-Bu
THF
4 °C to RT, 24 h, 91%
intermediate structure
intermediate structure intermediate structure
Tf2O, i-Pr2NEt
CH2Cl2
-78 °C, 90 min
intermediate structure
intermediate structure intermediate structure
Br3CCO2H
PhMe
-60 °C to RT, 23 h, 82%
intermediate structure
intermediate structure intermediate structure
Mg, CuBr.Me2S
THF
-50 °C to RT, 80 min, 58%
intermediate structure
intermediate structure intermediate structure
TiCl4
CH2Cl2
71%
intermediate structure
intermediate structure
TMS2NLi
THF
0 °C to RT, 100 min, 100%
intermediate structure
intermediate structure intermediate structure
t-BuLi, CuI, BF3.OEt2
Et2O, HMPT
-120 to -20 °C, 9 h, 60%
"The yield was 74 % brsm."
intermediate structure
intermediate structure intermediate structure
i-Pr2NLi, AcCl
THF, HMPA
-78 °C, 105 min, 86%
intermediate structure
intermediate structure intermediate structure
Li, CuI.Me2S
Et2O
-30 °C to RT, 2.5 h, 85%
"Also isolated was the C6'-epimer (5 % yield)."
intermediate structure
intermediate structure intermediate structure
AcOH
100 °C, 60 min, 63%
intermediate structure
intermediate structure intermediate structure
CuBr.Me2S
THF
-78 °C, 15 h
intermediate structure
intermediate structure intermediate structure
KOt-Bu
DMSO
RT to 100 °C, 10 h, 60%
intermediate structure
intermediate structure intermediate structure
NaOMe
MeOH
RT, 12 h, 58%
intermediate structure
intermediate structure
MeLi, CuI
-78 to -40 °C, 80 min, 93%
intermediate structure
intermediate structure
VinylMgBr
THF
-78 to 0 °C, 12.5 h, 90%
intermediate structure
intermediate structure
MeLi.LiBr, CuI
Et2O
0 °C, 30 min, 80%
intermediate structure
intermediate structure
VinylMgBr, CuI
THF
-78 °C to RT, 30 min, 55%
intermediate structure
intermediate structure
Methyl vinyl ketone, Et3N
MeOH
RT, 105 min, 74%
intermediate structure
intermediate structure
Me3N+Bn HO-
DME
-20 °C, 2.5 h, 44%
"Also isolated was the C2-epimer (14 % yield)."
intermediate structure
intermediate structure intermediate structure
K2CO3
MeCN
Reflux, 42 h, 95%
intermediate structure
intermediate structure
Methyl acrylate, Me3N+Bn HO-
Dioxane
50-70 °C, 60 min, 88%
intermediate structure
intermediate structure
Me2NH
H2O
0 °C, 2 h
intermediate structure