Stereospecific molecular rearrangement via nucleophilic substitution at quaternary stereocentres in acyclic systems
Kaushalendra Patel,
No information about this author
Ilan Marek
No information about this author
Nature Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 19, 2025
Language: Английский
Stereoinvertive SN1 Through Neighboring Group Participation
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(31)
Published: May 20, 2024
Abstract
Neighboring
group
participation,
the
assistance
of
non‐conjugated
electrons
to
a
reaction
center,
is
fundamental
phenomenon
in
chemistry.
In
framework
nucleophilic
substitution
reactions,
neighboring
participation
known
cause
rate
acceleration,
first
order
kinetics
(S
N
1),
and
retention
configuration.
The
latter
result
double
inversion:
one
when
displaces
leaving
group,
second
nucleophile
substitutes
group.
This
powerful
control
stereoretention
has
been
widely
used
organic
synthesis
for
more
than
century.
However,
may
also
lead
inversion
configuration,
which
often
overlooked.
Herein,
we
review
this
unique
mode
stereoinversion,
dividing
relevant
reactions
into
three
classes
with
aim
introduce
fresh
perspective
on
different
modes
stereoinversion
via
as
well
factors
that
stereochemical
outcome.
Language: Английский
Formally Stereoretentive SN1 Reactions of Homoallylic Tertiary Alcohols Via Nonclassical Carbocation
Kaushalendra Patel,
No information about this author
Leonie Wilczek,
No information about this author
Francesco Calogero
No information about this author
et al.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: May 27, 2025
We
present
a
stereoretentive
nucleophilic
substitution
of
homoallylic
tertiary
alcohols
via
the
formation
nonclassical
cyclopropyl
carbinyl
(CPC)
carbocation
intermediate.
This
strategy
enables
creation
highly
congested
centers
with
preserved
stereocontrol,
addressing
typical
challenges
instability
and
reactivity
in
SN1
mechanisms.
The
stabilization
CPC
intermediate
is
crucial
for
achieving
precise
regio-
stereoselectivity,
significantly
enhancing
utility
SN1-type
mechanisms
complex
molecule
synthesis.
Language: Английский
Stereoinvertive SN1 Through Neighboring Group Participation
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(31)
Published: May 20, 2024
Abstract
Neighboring
group
participation,
the
assistance
of
non‐conjugated
electrons
to
a
reaction
center,
is
fundamental
phenomenon
in
chemistry.
In
framework
nucleophilic
substitution
reactions,
neighboring
participation
known
cause
rate
acceleration,
first
order
kinetics
(S
N
1),
and
retention
configuration.
The
latter
result
double
inversion:
one
when
displaces
leaving
group,
second
nucleophile
substitutes
group.
This
powerful
control
stereoretention
has
been
widely
used
organic
synthesis
for
more
than
century.
However,
may
also
lead
inversion
configuration,
which
often
overlooked.
Herein,
we
review
this
unique
mode
stereoinversion,
dividing
relevant
reactions
into
three
classes
with
aim
introduce
fresh
perspective
on
different
modes
stereoinversion
via
as
well
factors
that
stereochemical
outcome.
Language: Английский