HoffmannRearrangement

DimaBerbasov
May, 1, 2009
May,1,2009
MSU
 Presentation Outline
PresentationOutline
Biography
Similarreactions
Recentapplications
li i
August Wilhelm von Hofmann
AugustWilhelmvonHofmann
Born 8 April 1818 Giessen, Germany

Alma mater University of Gottingen

Doctoral advisor Justus von Liebig

Doctoral students
Richard Abegg
Adolf Pinner
Fritz Haber
Karl Friedrich von Auwers
Rudolf Hugo Nietzki
Ferdinand Tiemann
Eugen Bamberger

Died
i d 5 May 1892 (aged
( d 74)
4) Berlin,
li Germany
G
 Major Discoveries
MajorDiscoveries
Hofmann
Hofmannwasthefirsttointroducemolecular
was the first to introduce molecular
modelsintohispubliclecturesaround1860
Hofmannelimination
Hofmann elimination
Hofmannsrule
Hofmannrearrangement
 Reaction Scheme
ReactionScheme

Firstpublished1881
Hofmann,A.W.Chem.Ber. 1881,14,2725.
Shioiri,T.Comp.Org.Syn. 1991,6,800806.(Review)
MechanismofHofmann
Rearrangement
Similar Reactions
SimilarReactions
Schmidt reaction
Schmidtreaction
Curtius Rearrangement
Lossen Rearrangement
 MildReplacementforBromine
O H
NBS, DBU N O
R
R NH2 MeOH,
MeOH O
reflux 45 min

R Yield, %

3,4-(MeO)2C6H3- 89
p-MeC6H4- 84
C6H5- 95
p-ClC6H4- 94
p-NO2-C6H4- 70
C6H5CH2- 95
CH3(CH2)8- 90

K ill J.
Keillor, J W
W.; Huang,
H X
X. Org.
O SSyntheses,
th 2004 Coll.
2004, C ll Vol.
V l 10,
10 549
 LTAasAlternative
toBasicConditions

Baumgarten, H. E.; Stalkis, A. J. Am. Chem. Soc. 1965, 87, 1141

Baumgarten, H. E.; Smith,
i h H. L.; Stalkis,
lki A. J. Org. Chem.
h 1975, 40, 3554
DegradationofLongChainAmides
throughHTIB
h h

Lazbin I. M.; Koser, G.F. J. Org. Chem. 1986, 51, 2669

 RoomTemperatureConditionsto
ReplacePIFA
l

Radhakrishna, A. S.; Rao, C.G.; Varma, B. B. Bhatnagar, S. P. Synthesis, 1983, 538

 APracticalSynthesisof()Oseltamivir
withPIFA
h

Satoh, N.; Akiba, T.; Yokoshima, S.; Fukuyama, T. Angew. Chem. Int. Ed. 2007, 46, 5734
Satoh, N.; Akiba, T.; Yokoshima, S.; Fukuyama, T. Tetrahedron, 2009, 65, 3239