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反応例 21.1 転位反応
電子不足炭素への転位
ピナコール転位
Me
MeMe
Me
OHHO
H2SO4
65-72%Me
Me
Me
OMe
G. A. Hill, E. W. Flosdorf, Org. Synth., Coll. Vol. 1, 462 (1941).
Ph
Ph Ph
Ph
OHHO
I2
AcOH
reflux
95-96%Ph
Ph
Ph
OPh
W. E. Bachmann, Org. Synth., Coll. Vol. 2, 73 (1943).
OH
OH
BF3O(nBu)2CHO
230 °C65-80%
J. P. Barnier, J. Champion, J. M. Conia, Org. Synth., Coll. Vol. 7, 129 (1990).
OEt
HO
HBF4O
66-75%
S. A. Miller, R. C. Gadwood, Org. Synth., Coll. Vol. 8, 556 (1993).
O
HO
O
O
Dowex-50W (H+)
rt, overnight
D. G. Hilmey, L. A. Paquette, Org. Synth., 84, 156 (2007).
OH
HCl
100 °C, 100 min
OH
M. Krumpolc, J. Rocek, Org. Synth., Coll. Vol. 7, 114 (1990).
Me MeMe
Pb(OAc)4, C6H6
65 °C, 1 h
Me MeMe
Me MeMe
AcO
AcO
R. S. Sivik, K. J. Stanton, L. A. Paquette, Org. Synth., Coll. Vol. 9, 745 (1998).
カルボニル化合物の転位
H5C6
O
H
C6H5
OH
NaBrO3, NaOH
85-90 °CH5C6
OH
CO2H
H5C6
84-90%
D. A. Ballard, W. M. Dehn, Org. Synth., Coll. Vol. 1, 89 (1941).
OH5C6
H
H
C6H5
BF3OEt2
H5C6CHO
H5C6
1 min74-82%
D. J. Reif, H. O. House., Org. Synth., Coll. Vol. 4, 375 (1963).
O
O
Me
MeMe
BF3OEt2 NaOH
MeMe
Me
O
MeMe
Me
O
CHO
56-63%
G. D. Ryerson, R. L. Wasson, H. O. House, Org. Synth., Coll. Vol. 4, 957 (1963).
H5C6C6H5
O
AlMetBu
tBu tBuBrBr
tBu
(H5C6)2CHCHO
-20 °C, 4 h 87%
T. Ooi, K. Maruoka, H. Yamamoto, Org. Synth., Coll. Vol. 9, 356 (1998).
Me
Me
Me Me
Me
Me
CF3CO3H, BF3OEt2
0 - 5 °C, 1 h
Me
Me Me
Me
Me
OMe
82-90%
H. Hart, R. M. Lange, P. M. Collins, Org. Synth., Coll. Vol. 5, 598 (1973).
Me
MeMe
Me
Me
Me
mCPBA
0-25 °C
Me
MeMe
Me
Me
Me
O
Me
Me
Me
Me
Me
Me
O
R. B. King, W. M. Douglas, A. Efraty, Org. Synth., Coll. Vol. 6, 39 (1988).
29-34%
電子不足の酸素，窒素への転位 Beckmann型転位
NOHH2SO4
NH
O
H2O H5C6COCl
NaOH
H5C6CONH(CH2)5CO2H
65-72%
J. C. Eck, C. S. Marvel, Org. Synth., Coll. Vol. 2, 76 (1943).
O
H2NOSO3H
HCO2H
reflux, 5 h
HN
O
72%
G. A. Olah, A. P. Fung, Org. Synth., Coll. Vol. 7, 254 (1990).
NOSO2Me
Pr3AlN Pr
DIBAL-HHN Pr
53-58%
K. Maruoka, S. Nakai, H. Yamamoto, Org. Synth., Coll. Vol. 8, 568 (1993).
Baeyer-Villiger転位
H. M. Walton, J. Org. Chem., 22, 1161 (1957).
O
C6H5
MeCO3H, AcOK
AcOHO
O
C6H5
62%
CHO H5C6CO3H
MeOH, H2O
CO2H
90%
Y. Ogata, Y. Sawaki, J. Org. Chem., 34, 3985 (1969).
O2N
O
MeCO3H
H2SO4, AcOHO
O2N
O
95%
W. von E. Doering, L. Speers, J. Am. Chem. Soc., 72, 5515 (1950).
COMe
H5C6CO3H
OCOMe
81%
J. A. Berson, S. Suzuki, J. Am. Chem. Soc., 81, 4088 (1959).
ヒドロペルオキシドの転位
OOHOH
OOHH2O2, H2SO4
H2O, 5~10 ̊ C
70% H2SO4
15~25 ̊ C
34~40%
J. Hoffman, Org. Synth., Coll. Vol. 5, 818 (1973).
カルベンの転位
COCl
Et3N, CH2N2
COCHN2
85-92%
H5C6CO2Ag
Et3N, EtOH
reflux, 1 h
CH2CO2Et
84-92%
V. Lee, M. S. Newman, Org. Synth., Coll. Vol. 6, 613 (1988).
tBuO NH
CO2H
OC6H5
ClCO2Et, Et3N CH2N2
N2
O
F3CCO2Ag, Et3N CO2H61-65%
M. R. Rinder, S. Steurer, J. Podlech, Org. Synth., Coll. Vol. 10, 194 (2004).
ニトレンの転位
MeO
MeO
CONH2 NaOCl, NaOH
50 - 70 °C, 1 h
MeO
MeO
NH2
J. S. Buck, W. S. Ide, Org. Synth., Coll. Vol. 2, 44 (1943).
80-82%
N
NH2
O
N
NH2Br2, 70 C̊
NaOH, H2O
65~71%
C.F.H. Allen, C.N. Wolf,
Org. Synth., Coll. Vol. 4, 45 (1963).
CO2H NaN3, H2SO4
50 °C, 1.5 h
NH2
60-80%
N. W. Werner, J. Casanova, Jr., Org. Synth., Coll. Vol. 5, 273 (1973).
Me NH2
O
Br2, NaOH
NH
NH
Me
O
Me
O
84-90%
E. D. AmStutz, R. R. Mters, Org. Synth., Coll. Vol. 2, 462 (1943).
HN
O O KOBr, KOH
H2O
41-45%H2N
CO2H
H. T. Clarke, L. D. Behr, Org. Synth., Coll. Vol. 2, 19 (1943).
CO2HClCO2Et
iPr2EtN
NaN3
CON3
H5C6CH2OH, toluene
reflux
NHCO2CH2C6H5 49-57%
P. J. Jessup, C. B. Petty, J. Roos, L. E. Overman, Org. Synth., Coll. Vol. 6, 95 (1988).
H5C6 CO2HEt3N
ClCO2Et
H5C6 CO2CO2EtNaN3
H5C6 CON3
H5C6 NCO
toluene
reflux
HCl NaOHH5C6 NH2
76-81%
C. Kaiser, J. Weinstock, Org. Synth., Coll. Vol. 6, 910 (1988).
N
CONH2
OMeKOCl, KOH
N
NH2
OMe50-58%
D. Enders, P. Fey, H. Kipphardt, Org. Synth., Coll. Vol. 8, 26 (1993).
CONH2
H5C6I(O2CCF3)2 HCl NH3Cl
69-77%
M. R. Almond, J. B. Stimmel, E. A. Thompson, G. M. Loudon, Org. Synth., Coll. Vol. 8, 132 (1993).
MeO
CONH2 NBS, DBU
MeOH
reflux, 45 minMeO
NHCO2Me
73%
J. W. Keillor, X. Huang, Org. Synth., Coll. Vol. 10, 549 (2004).
シグマトロピー転位
OMe
O reflux, 1 h
OMe
OH80-90%
C. F. H. Allen, J. W. Gates, Jr., Org. Synth., Coll. Vol. 3, 418 (1955).
O
O
TsOH
heat, 3 h
O
W. L. Howard, N. B. Lorette, Org. Synth., Coll. Vol. 5, 25 (1973).
85-91%
Me
Me
Me
Me
Me
HO
Hg(OAc)2OEt
reflux, 17 h
Me
O71%
220-225 °C, 5 h
Me
50-53%OHC
R. E. Ireland, D. J. Dawson, Org. Synth., Coll. Vol. 6, 298 (1988).
Hg(OAc)2OAc
OAc
75-77.5%
CO2MeMeO2C
AcO
AcOCO2Me
CO2Me
CO2Me
CO2Me
AcOOAc
41-49%
reflux, 6 h
R. M. Carlson, R. K. Hill, Org. Synth., Coll. Vol. 6, 196 (1988).
Me
Me
Me
Me
Me
HO
reflux, 65 h
Me
65%
R. E. Ireland, D. J. Dawson, Org. Synth., Coll. Vol. 6, 491 (1988).
Me
OMe
NMe2
OMe
o-xylene
O
Me2N
Me
Me
Me
Me
Me
HO
reflux
Me
49-60%
R. E. Ireland, D. J. Dawson, Org. Synth., Coll. Vol. 6, 584 (1988).O
Me2N
MeC(OEt)3
NH2
EtO
O
tBuOCl
-40 °CNHCl
MeSMe
-30 - -50 °C NH
SMe
Me Cl
Et3N
reflux, 16 h NH2
CH2SMe
34-37%
P. G. Gassman, G. Gruetzmacher, Org. Synth., Coll. Vol. 6, 581 (1988).
OH
MeMeC(OEt)3
propionic acid
138 - 140 °C
OEt
Me
O
83-88%
R. I. Trust, R. E. Ireland, Org. Synth., Coll. Vol. 6, 606 (1988).
OH
MeMeC(OEt)3
propionic acid
138 - 140 °C
OEt
Me
O
83-88%
R. I. Trust, R. E. Ireland, Org. Synth., Coll. Vol. 6, 606 (1988).
H5C6 OHhexanoic acid
100 - 166 °C, 6 h
MeC(OEt)3
KOH
CO2H
H5C6
F. B. Gonzalez, P. A. Bartlett, Org. Synth., Coll. Vol. 7, 164 (1990).
86-88%
R. G. Salomon, S. Ghosh, Org. Synth., Coll. Vol. 7, 177 (1990).
CHO OH
TsOH
OHC77-78%
CO2EtEt3N
Me3N CO2
HO Ph
NaH
H3O
OCO2H
C6H5
160 - 165 °C
76-82%
85%84-91%C6H5
CHO
D. E. Vogel, G. H. Buechi, Org. Synth., Coll. Vol. 8, 536 (1993).
Favorski 転位
O
Cl NaOMe
CO2Me
D.W. Goheen, W.R. Vaughan,
Org. Synth., Coll. Vol. 4, 594 (1963).Et2O, !
56~61%
O O
Br
Br
O
Br
Br
O
Br Br
–O OHOH–
H
CH3 CO2H
H
HO
O
Br2, 5˚C
48% HBr
1) KHCO3, H2O
2) HCl, H2O
69~77%
C. Rappe, Org. Synth., Coll. Vol. 6, 711 (1988).
