Preferred Label : sigmatropic rearrangement;
IUPAC definition : A molecular rearrangement that involves both the creation of a new σ-bond between
atoms previously not directly linked and the breaking of an existing σ-bond. There
is normally a concurrent relocation of π-bonds in the molecule concerned, but the
total number of π- and σ- bonds does not change. The term was originally restricted
to intramolecular pericyclic reactions, and many authors use it with this connotation.
It is, however, also applied in a more general, purely structural, sense. If such
reactions are intramolecular, their transition state may be visualized as an association
of two fragments connected at their termini by two partial σ-bonds, one being broken
and the other being formed as, for example, the two allyl fragments in (a'). Considering
only atoms within the (real or hypothetical) cyclic array undergoing reorganization,
if the numbers of these in the two fragments are designated i and j, then the rearrangement
is said to be a sigmatropic change of order [i, j] (conventionally [i] [j]). Thus
the rearrangement (a) is of order [3,3], whilst reaction (b) is a [1,5]sigmatropic
shift of hydrogen. (N.B. By convention square brackets [...] here refer to numbers
of atoms, in contrast with current usage in the context of cycloaddition.) The descriptors
a and s (antarafacial and antarafacial) may also be annexed to the numbers i and j;
(b) is then described as a [1s,5s] sigmatropic rearrangement, since it is suprafacial
with respect both to the hydrogen atom and to the pentadienyl system: The prefix
'homo' (meaning one extra atom, interrupting conjugation — i cf /i . 'homoaromaticity')
has frequently been applied to sigmatropic rearrangements, but is misleading.;
Origin ID : S05660;
See also
A molecular rearrangement that involves both the creation of a new σ-bond between
atoms previously not directly linked and the breaking of an existing σ-bond. There
is normally a concurrent relocation of π-bonds in the molecule concerned, but the
total number of π- and σ- bonds does not change. The term was originally restricted
to intramolecular pericyclic reactions, and many authors use it with this connotation.
It is, however, also applied in a more general, purely structural, sense. If such
reactions are intramolecular, their transition state may be visualized as an association
of two fragments connected at their termini by two partial σ-bonds, one being broken
and the other being formed as, for example, the two allyl fragments in (a'). Considering
only atoms within the (real or hypothetical) cyclic array undergoing reorganization,
if the numbers of these in the two fragments are designated i and j, then the rearrangement
is said to be a sigmatropic change of order [i, j] (conventionally [i] [j]). Thus
the rearrangement (a) is of order [3,3], whilst reaction (b) is a [1,5]sigmatropic
shift of hydrogen. (N.B. By convention square brackets [...] here refer to numbers
of atoms, in contrast with current usage in the context of cycloaddition.) The descriptors
a and s (antarafacial and antarafacial) may also be annexed to the numbers i and j;
(b) is then described as a [1s,5s] sigmatropic rearrangement, since it is suprafacial
with respect both to the hydrogen atom and to the pentadienyl system: The prefix
'homo' (meaning one extra atom, interrupting conjugation — i cf /i . 'homoaromaticity')
has frequently been applied to sigmatropic rearrangements, but is misleading.
