Rearrangement reactions

Table of Contents

In Organic Chemistry, one of the most relevant classes of reactions corresponds to rearrangement reactions, in which the carbon backbone of a molecule is rearranged to give a structural isomer of the original molecule. Frequently, a substituent is shifted from one atom to another in the same molecule. This section lists the most significant rearrangement named reactions in alphabetical order.

Allylic rearrangement

Allylic rearrangement

References:
L. Claisen, Chem. Ber. 45, 3157 (1912)

Algar-Flynn-Olyamada reaction

Algar-Flynn-Olyamada reaction

References:
J. Algar, J. P. Flynn, Proc. Roy. Irish Acad. 42B, I (1934)

Amadori rearrangement

Amadori rearrangement

M. Amadori, Atti Accad. Nazl. Lincei. 2(6), 337 (1925)

References:

Arndt-Eistert reaction

Arndt-Eistert reaction

References:
F. Arndt, B. Eistert, Chem. Ber. 68, 200 (1935)

Aza-Claisen rearrangement

Aza-Claisen rearrangement

References:
M. Diederich, U. Nubbemeyer, Angew. Chem. 107, 1095 (1995)
M. Diederich, U. Nubbemeyer, Angew. Chem. Int. Ed. Engl. 34, 1026z (1995)

Baeyer-Villiger oxidation

Baeyer-Villiger oxidation

References:
A. Baeyer, V. Villiger, Chem. Ber. 32, 3625 (1899)
A. Baeyer, V. Villiger, Chem. Ber. 33, 858 (1900)

Baker-Venkataraman rearrangement

Baker-Venkataraman rearrangement

References:
W. Baker, J. Chem. Soc. 1933, 1381

Barton reaction (Barton nitrite ester reaction)

Barton reaction (Barton nitrite ester reaction)

References:
D.H.R. Barton, J.M. Beaton, L.E. Geller, M.M. Pechet, J. Am. Chem. Soc. 82, 2640 (1960)
D.H.R. Barton, J.M. Beaton, L.E. Geller, M.M. Pechet, J. Am. Chem. Soc. 83, 4076 (1961)

Beckmann rearrangement

Beckmann rearrangement

References:
E. Beckmann, Chem. Ber. 19, 988 (1886)

Benzidine and semidine rearrangements

Benzidine and semidine rearrangements

References:
A.W. Hofmann, Proc. Roy. Soc. London 12, 576 (1863)

Benzilic acid rearrangement

Benzilic acid rearrangement

References:
J. Liebig, J. Liebigs Ann. Chem. 25, 27 (1838).

Bergman cyclization

Bergman cyclization

References:
R.R. Jones, R.G. Berman, J. Am. Chem. Soc, 94, 660 (1972)

Borsche–Drechsel cyclization

Borsche–Drechsel cyclization

References:
E. Drechsel, J. Prakt. Chem. 38, 69 (1858)
W. Borsche, M. Feise, Chem. Ber. 20, 378 (1904)

Brook rearrangement

Brook rearrangement

References:
A.G. Brook, J. Am. Chem. Soc. 80, 1886 (1958)
A.G. Brook, J. Am. Chem. Soc. 81, 981 (1959)

Carroll rearrangement

Carroll rearrangement

References:
M.F. Carroll, J. Chem. Soc. 1940, 704
M.F. Carroll, J. Chem. Soc. 1941, 507

Chapman rearrangement

Chapman rearrangement

References:
O. Mumm, H. Hesse, H. Volquartz, Chem. Ber., 48, 379 (1915)
A.W. Chapman, J. Chem. Soc. 1992, 127

Ciamician-Dennstedt rearrangement

Ciamician-Dennstedt rearrangement

References:
G.L. Ciamician, M. Dennstedt, Chem. Ber. 14, 1153 (1881)

Claisen rearrangement

Claisen rearrangement

References:
L. Claisen, Chem. Ber. 45, 3157 (1912)
L. Claisen, E. Tietze, Chem. Ber. 58, 275 (1925)
L. Claisen, E. Tietze, Chem. Ber. 59, 2344 (1926)

Cope rearrangement

Cope rearrangement

References:
A.C. Cope, E.M. Hardy, J. Am. Chem. Soc. 62, 441 (1940)
A.C. Cope, K.E. Hoyle, D. Heyl, J. Am. Chem. Soc. 63, 1843 (1941)
A.C. Cope, C.M. Hofmann, E.M. Hardy, J. Am. Chem. Soc. 63, 1852 (1941)
H. Levy, A.C. Cope, J. Am. Chem. Soc. 66, 1684 (1944)
E.G. Foster, A.C. Cope, F. Daniels, J. Am. Chem. Soc. 69, 1893 (1947)
A.C. Cope, L. Field, J. Am. Chem. Soc. 71, 1589 (1949)
A.C. Cope, P.H. Towle, J. Am. Chem. Soc. 71, 3423 (1949)
A.C. Cope, D.E. Morrison, L. Field, J. Am. Chem. Soc. 72, 59 (1950)

Cornforth rearrangement

Cornforth rearrangement

References:
J.W. Cornforth, The Chemistry of Penicillin (Princeton University Press, New Jersey, 1949) p 700

Curtius rearrangement (Curtius reaction or Curtius degradation)

Curtius rearrangement (Curtius reaction or Curtius degradation)

References:
T. Curtius, J. Prakt. Chem. 50. 275 (1894)

Demjanov rearrangement

Demjanov rearrangement

References:
N.J. Demjanov, M. Lushnikov, J. Russ. Phys. Chem. Soc. 35, 26 (1903)
N.J. Demjanov, M. Lushnikov, Chem. Zentr. 1903, I, 828
N.J. Demjanov, J. Russ. Phys. Chem. Soc. 36, 186 (1904)

D-Homo rearrangement of steroids

D-homo rearrangement occurs in the D-ring of steroids without carbon atoms loss.
It takes place in the D-ring of steroids, without carbon loss occurring. Upon treatment with bases or acids (Lewis acids) to the 17-hydroxy-20 derivatives, they rearrange and give six-membered D-rings.
This reaction also occurs when a carbocation is formed at position 20 without a carbonyl group. This rearrangement reaction is of great utility in the preparation of steroid derivatives.

D-Homo rearrangement of steroids

References:
L. Ruzicka, H. Meldahl, Helv. Chim. Acta 21, 1760 (1938)
L. Ruzicka, H. Meldahl, Helv. Chim. Acta 22, 421 (1939)

Dienol‐benzene rearrangement

Dienol‐benzene rearrangement

References:
H. Plieninger, G. Keilich, Angew. Chem. 68, 618 (1956);
H. Plieninger, G. Keilich, Chem. Ber. 91, 1891 1958)
M.J. Gentles, J.B. Moss, H.L. Herzog, E.B. Hershberg, J. Am. Chem. Soc. 80, 3702 (1958)

Dienone-phenol rearrangement

Dienone-phenol rearrangement

References:
K. von Auwers, K. Ziegler, Ann. 425, 217 (1921)
H.H. Inhoffen et at., Naturwissenschaften 26, 756 (1938)
H.H. Inhoffen et at., Ann. 563, 177 (1949)

Dimroth rearrangement

Dimroth rearrangement

References:
O. Dimroth, Ann. 364, 183 (1909);
O. Dimroth, Ann. 459, 39 (1927).

Favorskii rearrangement

Favorskii rearrangement

References:
A. E. Favorskii, J. Ptakt. Chem. [2] 88, 658 (1913)
A. E. Favorskii and V. N. Bozhovskii, J. Russ. Phys. Chem. Soc. 46, 1097 (1914)
C.A. 9, 1900 (1915); O. Wallach, Ann. 414, 296 (1918)

Fischer indole synthesis

Fischer indole synthesis

References:
E. Fischer, F. Jourdan, Chem. Ber. 16, 2241 (1883)
E. Fischer, O. Hess, Chem. Ber. 17, 559 (1884)

Fischer-Hepp rearrangement

Fischer-Hepp rearrangement

References:
E. Fischer, E. Hepp, Chem. Ber. 19, 2991 (1886)

Fries rearrangement

Fritsch–Buttenberg–Wiechell rearrangement

Fritsch–Buttenberg–Wiechell rearrangement

References:
P. Fritsch, J. Liebigs Ann. Chem. 279, 319 (1894)
W.P. Buttenberg, J. Liebigs Ann. Chem. 279, 327 (1894)
H. Wiechell, J. Liebigs Ann. Chem. 279, 332 (1894)

Gabriel-Coleman rearrangement (Isoquinoline synthesis of)

Gabriel-Coleman rearrangement (Isoquinoline synthesis of)

References:

Hayashi rearrangement

Hayashi rearrangement

References:

HERON Rearrangement (Heteroatom Rearrangements on Nitrogen)

HERON Rearrangement (Heteroatom Rearrangements on Nitrogen)

References:

Hofmann rearrangement (Hofmann degradation)

Hofmann rearrangement (Hofmann degradation)

References:

Hofmann–Löffler reaction (Hofmann–Löffler–Freytag reaction)

Hofmann–Löffler reaction (Hofmann–Löffler–Freytag reaction)

References:

Ladenburg rearrangement

Ladenburg rearrangement

References:

Lossen rearrangement

Lossen rearrangement

References:

McLafferty rearrangement

McLafferty rearrangement

References:

Meisenheimer rearrangement

Meisenheimer rearrangement

References:

Mislow–Evans rearrangement

Mislow–Evans rearrangement

References:

Moore-Myers cyclization

Moore-Myers cyclization

References:

Nametkin rearrangement

Nametkin rearrangement

References:

Neber rearrangement

Neber rearrangement

References:

Overman rearrangement

Overman rearrangement

References:

Perkin rearrangement (coumarin benzofuran ring contraction)

Perkin rearrangement (coumarin benzofuran ring contraction)

References:

Reagrupamiento Retropinacol

References:

Rowe rearrangement

Rowe rearrangement

References:

Schmidt reaction

Schmidt reaction

References:

Stevens rearrangement

Stevens rearrangement

References:

Stieglitz rearrangement

Stieglitz rearrangement

References:

Tafel rearrangement

Tafel rearrangement

References:

Tiemann rearrangement

Tiemann rearrangement

References:

Tiffeneau–Demjanov rearrangement (TDR) (ring expansion)

Tiffeneau–Demjanov rearrangement (TDR) (ring expansion)

References:

Truce-Smiles rearrangement

Truce-Smiles rearrangement

References:

Wagner-Meerwein rearrangement

Wagner-Meerwein rearrangement

References:

Wallach rearrangement

Wallach rearrangement

References:

Wessely-Moser rearrangement

Wessely-Moser rearrangement

References:

Westphalen-Lettré rearrangement

Westphalen-Lettré rearrangement

References:

1,2-Wittig rearrangement

1,2-Wittig rearrangement

References:
G. Wittig, L. Lohmann, Ann. 550, 260 (1942)
G. Wittig, Experientia 14, 389 (1958)

2,3-Wittig rearrangement

2,3-Wittig rearrangement

References:
J. Cast, T.S. Stevens, J. Holmes, J. Chem. Soc. 1960, 3521
U. Schollkopf, K. Fellenberger, Chem. Ber. 698, 80 (1966)
Y. Makisumi, S. Noltzumoto, Tetrahedron Letters 1966, 6393
K. Mikami, T. Nakai, Synthesis 1994, 594

Wolff rearrangement

Wolff rearrangement

References:

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