Rhodium‐Catalyzed Enantio‐ and Regioselective Allylation of Indoles with gem‐Difluorinated Cyclopropanes
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(22)
Опубликована: Март 22, 2024
Abstract
The
use
of
gem
‐difluorinated
cyclopropanes
(
‐DFCPs)
as
fluoroallyl
surrogates
under
transition‐metal
catalysis
has
drawn
considerable
attention
recently
but
such
reactions
are
restricted
to
producing
achiral
or
racemic
mono‐fluoroalkenes.
Herein,
we
report
the
first
enantioselective
allylation
indoles
rhodium
with
‐DFCPs.
This
reaction
shows
exceptional
branched
regioselectivity
towards
‐DFCPs,
which
provides
an
efficient
route
enantioenriched
fluoroallylated
wide
substrate
scope
and
good
functional
group
tolerance.
Язык: Английский
High‐Valent Copper Catalysis Enables Regioselective Fluoroarylation of Gem‐Difluorinated Cyclopropanes
Advanced Science,
Год журнала:
2024,
Номер
11(18)
Опубликована: Март 9, 2024
Abstract
Transition‐metal
(TM)
catalyzed
reaction
of
gem
‐difluorinated
cyclopropanes
(
‐DFCPs)
has
drawn
much
attention
recently.
The
generally
occurs
via
the
activation
distal
C─C
bond
in
‐DFCPs
by
a
low‐valent
TM
through
oxidative
addition,
eventually
producing
mono‐fluoro
olefins
as
coupling
products.
However,
achieving
regioselective
proximal
that
overcomes
intrinsic
reactivity
catalysis
remains
elusive.
Here,
new
mode
enabled
high‐valent
copper
catalysis,
which
allows
exclusive
congested
is
presented.
achieves
fluoroarylation
uses
NFSI
(N‐fluorobenzenesulfonimide)
electrophilic
fluoro
reagent
and
arenes
C─H
nucleophiles,
enabling
synthesis
diverse
CF
3
‐containing
scaffolds.
It
proposed
species
plays
an
important
role
possibly
σ‐bond
metathesis.
Язык: Английский
Double strain-release enables formal C–O/C–F and C–N/C–F ring-opening metathesis
Yulei Zhu,
Jie Jia,
Xiangyu Song
и другие.
Chemical Science,
Год журнала:
2024,
Номер
15(34), С. 13800 - 13806
Опубликована: Янв. 1, 2024
Metathesis
reactions
have
been
established
as
a
powerful
tool
in
organic
synthesis.
While
great
advances
were
achieved
double-bond
metathesis,
like
olefin
metathesis
and
carbonyl
single-bond
has
received
less
attention
the
past
decade.
Herein,
we
describe
first
C(sp
Язык: Английский
Rhodium‐Catalyzed Enantio‐ and Regioselective Allylation of Indoles with gem‐Difluorinated Cyclopropanes
Angewandte Chemie,
Год журнала:
2024,
Номер
136(22)
Опубликована: Март 22, 2024
Abstract
The
use
of
gem
‐difluorinated
cyclopropanes
(
‐DFCPs)
as
fluoroallyl
surrogates
under
transition‐metal
catalysis
has
drawn
considerable
attention
recently
but
such
reactions
are
restricted
to
producing
achiral
or
racemic
mono‐fluoroalkenes.
Herein,
we
report
the
first
enantioselective
allylation
indoles
rhodium
with
‐DFCPs.
This
reaction
shows
exceptional
branched
regioselectivity
towards
‐DFCPs,
which
provides
an
efficient
route
enantioenriched
fluoroallylated
wide
substrate
scope
and
good
functional
group
tolerance.
Язык: Английский
Fluoro-Promoted Thermal Ring Expansion of Cyclopropyl Carbenes to gem-Difluorinated Cyclobutenes
Organic Letters,
Год журнала:
2024,
Номер
26(48), С. 10317 - 10321
Опубликована: Ноя. 21, 2024
Synthesis
of
Язык: Английский
Photoredox-Catalyzed Regioselective 1,3-Alkoxypyridylation of gem-Difluorocyclopropanes
Organic Letters,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 4, 2024
Difluoromethylene
and
pyridine
cores
are
very
important
structural
units
in
medicinal
chemistry.
Herein,
we
report
the
development
of
photoredox-catalyzed
ring-opening
1,3-alkoxypyridylation
gem-difluorinated
cyclopropanes
using
4-cyanopyrines
alcohols,
employing
cyclopropane
radical
cations
as
key
intermediate.
The
reaction
exhibits
high
regioselectivity
under
mild
conditions
can
also
be
practiced
on
gram-scale
synthesis,
telescoped
reaction,
late-stage
functionalization
biological
molecules.
Язык: Английский