Abstract
Traditional
palladium‐catalyzed
dearomatization
of
(hetero)arenes
takes
place
via
an
ionic
pathway
and
usually
requires
elevated
temperatures
to
overcome
the
energy
barrier
dearomative
insertion
step.
Herein,
a
combination
radical
two‐electron
pathways
is
disclosed,
which
enables
room
temperature
3D
transformations
nonactivated
phenyl
rings
with
Pd(0)
as
catalyst.
Experimental
results
together
density
functional
theory
(DFT)
calculations
indicate
versatile
π‐allyl
Pd(II)
species,
cyclohexadienyl
Pd(II),
possibly
involved
in
dearomatization.
This
species
generated
by
combining
Pd(I).
The
provides
chemoselective
(carboamination
trieneylation),
regioselective
(1,2‐carboamination),
diastereoselective
(carbonyl‐group
directed
face
selectivity)
conversions.
ACS Catalysis,
Год журнала:
2022,
Номер
12(3), С. 2058 - 2063
Опубликована: Янв. 24, 2022
A
preeminent
challenge
in
alkene
difunctionalization
is
the
control
of
regio-,
diastereo-,
and
enantioselectivity.
In
this
Perspective,
a
Pd/Cu-cooperative
catalytic
system
for
arylboration
highlighted
that
allows
controlled
introduction
substituents.
particular,
examples
allowed
divergent
reactivity
from
single
substrate
based
on
tuning
catalysts
reaction
conditions
are
emphasized.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(13), С. 5985 - 5995
Опубликована: Март 26, 2022
The
selective
reductive
coupling
of
vinyl
heteroarenes
with
aldehydes
and
ketones
represents
a
versatile
approach
for
the
rapid
construction
enantiomerically
enriched
secondary
tertiary
alcohols,
respectively.
Herein,
we
demonstrate
CuH-catalyzed
regiodivergent
carbonyl-containing
electrophiles,
in
which
selectivity
is
controlled
by
ancillary
ligand.
This
leverages
an
situ
generated
benzyl-
or
dearomatized
allyl-Cu
intermediate,
yielding
either
exocyclic
addition
products,
method
exhibits
excellent
regio-,
diastereo-,
enantioselectivity
tolerates
range
common
functional
groups
heterocycles.
dearomative
pathway
allows
direct
access
to
variety
functionalized
saturated
heterocyclic
structures.
reaction
mechanism
was
probed
using
combination
experimental
computational
approach.
Density
theory
studies
suggest
that
ligand-controlled
regioselectivity
results
from
C-H/π
interaction
steric
repulsion
transition
states,
leading
major
minor
regioisomers,
Hydrocupration
heteroarene
pronucleophile
enantiodetermining
step,
whereas
diastereoselectivity
enforced
interactions
between
benzylic
intermediate
substrates
six-membered
cyclic
state.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(46)
Опубликована: Окт. 17, 2022
Two
catalytic
systems
have
been
developed
for
the
arylboration
of
endocyclic
enecarbamates
to
deliver
synthetically
versatile
borylated
saturated
N-heterocycles
in
good
regio-
and
diastereoselectivities.
A
Cu/Pd
dual
reaction
enables
synthesis
borylated,
α-arylated
azetidines,
while
a
Ni-catalysed
efficiently
functionalizes
5-,
6-,
7-membered
enecarbamates.
In
case
Cu/Pd-system,
remarkable
additive
effect
was
identified
that
allowed
broader
scope.
The
products
are
useful,
as
demonstrated
by
manipulations
boronic
ester
access
biologically
active
compounds.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(28), С. 18866 - 18872
Опубликована: Июль 5, 2024
C-Glycosides
are
important
structures
that
common
to
natural
products
and
pharmaceutical
agents.
Established
methods
for
their
synthesis
involve
the
reaction
of
an
activated
anomeric
carbon.
In
this
study,
we
report
a
conceptually
new
approach
involves
stereoselective
Ni-catalyzed
carboboration
glycals.
these
reactions,
not
only
is
C–C
bond
formed
at
carbon,
but
synthetically
useful
C–B
also
installed.
Upon
oxidation,
differentially
protected
C-glycosides
be
formed.
addition,
stereospecific
manipulation
leads
diverse
C-glycosides.
Finally,
application
method
in
established
C-glycosides,
such
as
C-glycosyl
amino
acids,
well
strategy
make
all
possible
diastereomers
C1
C2.
Asian Journal of Organic Chemistry,
Год журнала:
2022,
Номер
11(10)
Опубликована: Авг. 3, 2022
Abstract
Polycyclic
fused
indoline
derivatives,
specifically
those
bearing
tertiary
or
quaternary
carbon
stereocenters
at
C2
and
C3
positions,
stand
as
an
important
class
of
nitrogen‐containing
heterocyclic
compounds
because
they
are
frequently
occurring
core
structures
in
a
wide
variety
alkaloid
natural
products,
pharmaceutical
molecules,
functional
materials.
Over
the
past
few
decades,
development
new
versatile
synthetic
approaches
for
construction
indolines
has
been
focus
great
deal
research
initiatives.
In
this
review,
recent
advances
dearomative
annulation
N‐
acylindoles
with
diverse
nucleophiles
summarized
since
2012,
which
could
be
divided
into
five
categories:
1)
Dearomative
Heck
reactions
acylindoles;
2)
Visible‐light‐induced
reductive
dearomatization
3)
Lewis
acid‐catalyzed
4)
Asymmetric
5)
by
other
closely
related
reagents.
Chemistry - A European Journal,
Год журнала:
2022,
Номер
28(42)
Опубликована: Май 19, 2022
We
developed
time-atom
economic
regio-
and
chemoselective
sulfonyl
radical
triggered
5-exo-dig
cyclization
of
unactivated
1,6-enynes
with
halides
under
metal,
additive-free
reaction
conditions
to
achieve
highly
substituted
five-membered
heterocyclic
compounds.
This
transformation
creates
three
new
bonds,
such
as
C-SO2
,
C-C,
active
C-I/Br
bonds.
Importantly,
one-pot
protocols
produce
desired
products
directly
from
sodium
sulfinates
have
an
additional
advantage
minimising
chemical
waste,
saving
time,
simplifying
practical
aspects
compared
existing
protocols.
Abstract
In
contrast
to
the
considerable
progress
in
development
of
methodologies
for
amide
bond
formation
amines,
direct
N
‐acylation
less
nucleophilic
‐heterocycles
and
amides
with
carboxylic
acids
is
still
challenging.
this
report,
we
describe
heterocycles
promoted
by
4‐(
,
‐dimethylamino)pyridine
‐oxide
(DMAPO)/di‐
tert
‐butyl
dicarbonate
(Boc
2
O)
system.
The
new
one‐pot
method,
which
does
not
involve
pre‐activation
substrates,
enables
a
wide
variety
nitrogen
nucleophiles
such
as
indole,
carbazole,
pyrrole,
pyrazole,
lactam,
oxazolidinone,
anilide
high
yield.
method
also
exhibits
excellent
functional
group
tolerance
broad
substrate
scope.
As
present
practical,
operationally
simple,
scalable,
it
should
find
applications
both
academic
industrial
laboratories.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(13)
Опубликована: Янв. 26, 2022
Abstract
Dearomatized
indole
derivatives
bearing
a
C3‐
or
C2‐stereocenter
exist
ubiquitously
in
natural
products
and
biologically
active
molecules.
Despite
remarkable
advances
their
synthesis,
stereoselective
regio‐divergent
methods
are
still
high
demand.
Herein,
Pd‐catalyzed
intermolecular
asymmetric
spiroannulation
of
2,3‐disubstituted
indoles
with
internal
alkynes
has
been
developed
for
the
efficient
construction
indoline
structures
C2‐quaternary
stereocenter.
Stereospecific
aza‐semipinacol
rearrangement
these
under
acidic
conditions
afforded
indolenine
C3‐quaternary
stereocenter,
where
migrating
group
could
be
controlled
by
reaction
sequence.
The
together
subsequent
enabled
divergent
access
to
dearomatized
either
Organic Process Research & Development,
Год журнала:
2022,
Номер
26(8), С. 2281 - 2310
Опубликована: Авг. 2, 2022
This
review
provides
a
summary
of
recently
published
developments
in
the
field
nonprecious
metal
catalysis
(NPMC)
and
highlights
range
synthetic
applications
captured
research
between
July
October
2021.
is
an
installment
series
on
this
area
briefing
Ni,
Cu,
Fe,
Co
catalysis.
There
has
been
evident
increase
publications
NPMC,
which
indicates
widespread
interest
among
laboratories
academia
industry
development
utilization
catalytic
these
metals.
Organic & Biomolecular Chemistry,
Год журнала:
2022,
Номер
20(47), С. 9255 - 9271
Опубликована: Янв. 1, 2022
This
Review
provides
the
community
with
a
comprehensive
summary
of
application
Ni-catalyzed
carboboration
strategy
by
carefully
classifying
reaction
types
and
detailing
useful
examples.
