Organic Chemistry Frontiers,
Год журнала:
2023,
Номер
10(7), С. 1633 - 1642
Опубликована: Янв. 1, 2023
A
visible
light-driven
dearomatization
of
an
N
-(
o
-haloarylformyl)indole
in
electron
donor–acceptor
(EDA)
complex
with
a
thiophenol.
The
radical
reaction
is
terminated
by
concerted
hydrogen
atom
transfer
(HAT).
Nature Communications,
Год журнала:
2023,
Номер
14(1)
Опубликована: Апрель 20, 2023
Chiral
polycyclic
indolines
are
widely
present
in
natural
products
and
have
become
the
focus
of
extensive
synthetic
efforts.
Here,
we
show
catalytic
asymmetric
dearomative
[3
+
2]
annulation
indoles
with
donor-acceptor
aminocyclopropanes
to
construct
tricyclic
indolines.
Key
success
reaction
is
rational
design
C1-symmetric
bifunctional
tridentate
imidazoline-pyrroloimidazolone
pyridine
ligand.
Under
5
mol%
Ni(OTf)2-ligand
complex,
diverse
containing
cyclopentamine
moieties
obtained
good
chemoselectivities,
high
diastereoselectivities,
excellent
enantioselectivities.
An
unusual
cis-configuration
ligand
superior
trans-configuration
corresponding
C2-symmetric
nitrogen
ligands
reaction.
Mechanistic
studies
by
control
experiments
density
functional
theory
calculations
reveal
a
dual
activation
manner,
where
Ni(II)
complex
activates
aminocyclopropane
via
coordination
geminal
diester,
imidazolidine
NH
forms
H-bond
succinimide
moiety.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(35)
Опубликована: Май 16, 2024
Abstract
The
construction
of
chiral
motifs
containing
nonadjacent
stereocenters
in
an
enantio‐
and
diastereoselective
manner
has
long
been
a
challenging
task
synthetic
chemistry,
especially
with
respect
to
their
stereodivergent
synthesis.
Herein,
we
describe
protocol
that
enables
the
1,5/1,7‐nonadjacent
tetrasubstituted
through
Pd/Cu‐cocatalyzed
Heck
cascade
reaction.
Notably,
C=C
bond
relay
strategy
involving
shift
π‐allyl
palladium
intermediate
was
successfully
applied
asymmetric
1,7‐nonadjacent
stereocenters.
current
method
allows
for
efficient
preparation
molecules
bearing
two
privileged
scaffolds,
oxindoles
non‐natural
α‐amino
acids,
good
functional
group
tolerance.
full
complement
four
stereoisomers
products
could
be
readily
accessed
by
simple
combination
metal
catalysts
different
enantiomers.
Organic Letters,
Год журнала:
2024,
Номер
26(5), С. 1083 - 1087
Опубликована: Янв. 26, 2024
We
report
an
efficient
and
mild
approach
for
radical
dearomatization
via
photoinduced
palladium-catalyzed
reaction
of
three
components
(i.e.,
furans,
alcohols,
bromoalkanes).
In
this
strategy,
various
functionalized
spiro-heterocycles
were
prepared
from
furans
in
one
step
cascade
C–C/C–O
bond
formation
under
redox
neutral
conditions.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(24), С. 16892 - 16901
Опубликована: Июнь 6, 2024
The
development
of
a
catalytic
method
for
stereogenic
carbon
center
formation
holds
immense
significance
in
organic
synthesis.
Transition-metal-catalyzed
cross-coupling
reaction
has
been
regarded
as
straightforward
and
efficient
tool
stereoselectively
forging
C–C
bond.
Nevertheless,
the
creation
acyclic
all-carbon
quaternary-containing
vicinal
stereocenters
remains
notoriously
challenging
within
domain
chemistry
despite
their
prominence
various
bioactive
small
molecules.
Herein,
we
describe
palladium-catalyzed
asymmetric
multicomponent
trisubstituted
alkene
with
aryl
diazonium
salts
arylboronic
acids
to
realize
tertiary-quaternary
centers
high
regio-,
distereo-,
enantioselectivity.
Specifically,
precise
manipulation
stereoconfiguration
alkenes
enables
divergent
stereoselective
reaction,
thus
allowing
facile
construction
all
four
enantiomers.
Harnessing
ligand-swap
strategy
involving
chiral
bisoxazoline
an
achiral
fumarate
individually
accelerates
enantioselective
migratory
insertion
reductive
elimination
step
process,
supported
by
density
functional
theory
(DFT)
calculations,
obviating
requirement
neighboring
directing
group
internal
olefin
skeleton.
Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
365(5), С. 620 - 681
Опубликована: Янв. 17, 2023
Abstract
This
review
updates
the
field
of
enantioselective
domino
reactions
promoted
by
chiral
catalysts
derived
from
noble
metals,
including
palladium,
silver,
rhodium,
ruthenium,
iridium
and
gold,
published
since
beginning
2019.
It
illustrates
how
much
a
diversity
these
allow
unprecedented
asymmetric
many
types
to
be
achieved
with
excellent
enantioselectivity,
giving
direct
access
wide
variety
complex
molecules.
magnified
image
ACS Catalysis,
Год журнала:
2023,
Номер
13(7), С. 4873 - 4881
Опубликована: Март 27, 2023
The
divergent
catalytic
reactions
based
on
C–C
activation
of
benzocyclobutenones
have
been
discovered,
consisting
a
highly
enantioselective
dearomatic
"Cut
&
Sew"
transformation
and
cascade
C–C/C–H
activation/annulation
process.
asymmetric
dearomatization
was
achieved
with
2.5
mol
%
[Rh(HQ)(cod)]BF4
3
(S)-dtbm-Segphos,
leading
to
variety
enantioenriched
polyfused
rings
(21
examples,
up
99%
yield
enantiometric
excess
(ee)).
While
the
tandem
yields
series
amide-linked
biaryl
tricycles
(29
89%
yield)
through
net
C1–C2
bond
Caryl–H
metathesis.
A
detailed
density
functional
theory
(DFT)
computation
revealed
that
an
amide-directed
regioselective
Rh
complex
is
realized,
in
contrast
known
C1–C8
cleavage.
origins
were
further
elucidated.
ACS Catalysis,
Год журнала:
2023,
Номер
13(17), С. 11528 - 11540
Опубликована: Авг. 16, 2023
A
highly
enantioselective
dearomative
[3
+
2]
annulation
of
quinolines,
isoquinolines,
and
pyridines
with
donor–acceptor
aminocyclopropanes
was
achieved.
With
C1-symmetric
imidazoline-pyrroloimidazolone
pyridine
as
the
tridentate
ligand
Co(OTf)2
Lewis
acid,
diverse
chiral
indolizidine
benzo-fused
derivatives
were
obtained
in
good
yields
(up
to
98%
yield),
excellent
diastereoselectivities
(>20:1
dr),
enantioselectivities
ee).
Mechanistic
experiments
density
functional
theory
(DFT)
calculations
revealed
that
nitrogen
acted
a
bifunctional
ligand.
The
not
only
coordinated
Co(II)
salt
activate
aminocyclopropane
via
bidentate
coordination,
but
also
formed
H-bond
oxygen
atom
succinimide
moiety
fix
orientation
aminocyclopropane,
thus
facilitating
nucleophilic
attack
N-heteroaromatics.
Additionally,
high
enantioselectivity
reaction
governed
by
steric
factors.
Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
365(15), С. 2436 - 2466
Опубликована: Июнь 12, 2023
Abstract
Elaborated
molecular
architectures
including
complex
carbocycles,
heterocycles,
and
polycyclic
structures
represent
an
important
class
of
organic
compounds
because
they
are
ubiquitous
structural
units
in
a
broad
variety
biologically
pharmacologically
relevant
natural
products,
medicinal
molecules,
functional
materials.
A
major
challenge
modern
synthetic
methodology
is
the
development
strategically
efficient
selective
construction
these
from
readily
available
starting
Transition‐metal‐catalyzed
transformations
involving
Heck
reaction
as
pivotal
step
have
afforded
powerful
approach
for
accessing
sophisticated
skeletons
set
easy‐to
handle
materials,
thus
highlighting
its
potential
significance
streamlining
drug
discovery
process.
Over
past
few
decades,
significant
effort
has
been
devoted
to
derivatives
versatile
routes,
number
direct
strategies
reported.
In
this
review,
latest
advances
transition‐metal‐catalyzed
critical
summarized,
which
could
be
divided
into
six
categories:
1)
Heck/Sonogashira
tandem
reaction;
2)
Heck/Suzuki
3)
Heck/Heck
4)
Heck/Hiyama
5)
Heck/Cacchi
6)
Heck/C−H
bond
functionalization
reaction.