ACS Catalysis,
Год журнала:
2024,
Номер
14(8), С. 5847 - 5857
Опубликована: Апрель 2, 2024
An
Ir(III)
complex
catalyzed
single
and
dual
reductive
amination
followed
by
N-methylation
of
aldehydes
ketones
to
synthesize
N,N-dimethyl
as
well
N-methyl
tertiary
amines,
respectively,
utilizing
ammonium
formate
methanol
N1
C1
sources
is
reported.
The
protocol
was
efficiently
extended
a
tandem
amination/N-methylation/cyclization
keto
acids/esters
leading
lactams.
A
broad
substrate
scope,
synthesis
bioactive
molecules,
also
demonstrated.
Control
experiments,
kinetic
studies,
DFT
calculations
were
performed
based
on
which
plausible
mechanism
proposed.
Accounts of Chemical Research,
Год журнала:
2021,
Номер
54(11), С. 2683 - 2700
Опубликована: Май 12, 2021
ConspectusCatalytic
reactions
that
construct
carbon–nitrogen
bonds
are
one
of
central
themes
in
both
synthetic
and
medicinal
chemistry
since
the
obtainable
nitrogen-containing
motifs
commonly
encountered
natural
products
have
also
seen
a
growing
prominence
as
key
structural
features
marketed
drugs
preclinical
candidates.
Pd-catalyzed
cross-couplings,
such
Buchwald–Hartwig
amination,
at
forefront
methods
practical
settings.
However,
they
require
prefunctionalized
substrates
(hetero)aryl
halides
must
be
prepared
independently,
often
by
multiple
operations.
One
emerging
way
to
circumvent
these
preparatory
steps
directly
convert
ubiquitous
C–H
into
valuable
C–N
is
catalytic
which
allows
chemists
devise
shorter
more
efficient
retrosynthetic
schemes.
The
past
two
decades
witnessed
considerable
progress
expanding
repertoire
this
strategy,
especially
identifying
effective
amino
group
precursors.
In
context,
dioxazolones
experienced
dramatic
resurgence
recent
years
versatile
nitrogen
source
combination
with
transition-metal
catalyst
systems
facilitate
decarboxylation
access
metal-acylnitrenoid
intermediates.
addition
their
high
robustness
easy
accessibility
from
abundant
carboxylic
acids,
unique
reactivity
transient
intermediates
amido
transfer
has
led
fruitful
journey
for
mild
amidation
reactions.This
Account
summarizes
our
contributions
development
bond-forming
using
nitrenoid
precursors,
categorized
subsets
according
mechanistic
differences:
inner-
versus
outer-sphere
pathways.
first
section
describes
how
we
could
unveil
potential
realm
inner-sphere
amidation,
where
demonstrated
serve
not
only
manageable
alternatives
acyl
azides
but
highly
reagents
significantly
reduce
loading
temperature.
Taking
advantage
conditions
9
Cp*M
complexes
(M
=
Rh,
Ir,
Co)
or
isoelectronic
Ru
species,
dramatically
expanded
accessible
scope.
Mechanistic
investigations
revealed
putative
metal-nitrenoid
species
involved
intermediate
during
catalysis,
leads
facile
bond
formation.
On
basis
underpinning,
succeeded
developing
novel
platforms
harness
intermediacy
metal-nitrenoids
explore
insertion
via
an
pathway.
Indeed,
tailored
catalysts
were
capable
suppressing
competitive
Curtius-type
decomposition,
thus
granting
lactam
products.
We
further
repurposed
upon
modification
chelating
ligands
identity
transition
metal
achieve
three
goals:
(i)
addressing
selectivity
issues
control
regio-,
chemo-,
enantioselectivities,
(ii)
sustainable
catalysis
first-low
metals,
(iii)
navigating
chemical
space
(di)functionalization
alkenes/alkynes.
Together
own
research
efforts,
highlighted
herein
some
important
relevant
advances
other
groups.
finally
conclude
brief
overview
eye
toward
developments.
Chemical Reviews,
Год журнала:
2023,
Номер
123(8), С. 4764 - 4794
Опубликована: Март 29, 2023
Chiral
transition
metal
catalysts
represent
a
powerful
and
economic
tool
for
implementing
stereocenters
in
organic
synthesis,
with
the
center
providing
strong
chemical
activation
upon
its
interaction
substrates
or
reagents,
while
overall
chirality
of
complex
achieves
desired
stereoselectivity.
Often,
chiral
topology
implements
stereogenic
center,
which
is
then
involved
origin
asymmetric
induction.
This
review
provides
comprehensive
survey
reported
formally
constitutes
stereocenter.
A
goes
along
an
complex,
regardless
whether
ligands
are
achiral.
Implications
catalyst
design
mechanism
induction
discussed
half-sandwich,
tetracoordinated,
pentacoordinated,
hexacoordinated
complexes
containing
center.
The
distinguishes
between
originating
from
coordination
to
those
solely
composed
optically
inactive
(achiral
rapidly
interconverting
enantiomers)
prior
complexation
(dubbed
“chiral-at-metal”
catalysts).
Journal of the American Chemical Society,
Год журнала:
2021,
Номер
143(17), С. 6363 - 6369
Опубликована: Апрель 22, 2021
Described
herein
is
the
Ir-catalyzed
enantioselective
access
to
chiral
spirolactam
products
via
nitrenoid
transfer
aromatic
ipso-carbons.
The
key
strategy
for
precise
stereocontrol
enhance
secondary
attractive
and
repulsive
interactions
between
catalyst
substrates
by
introduction
of
a
traceless
O-silyl
achiral
auxiliary,
thus
effectively
differentiating
two
prochiral
faces
arenol-derived
1,4,2-dioxazol-5-one
substrates.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(22), С. 10064 - 10074
Опубликована: Май 27, 2022
Intramolecular
alkyne
hydroamidation
represents
a
straightforward
approach
for
the
access
to
synthetically
valuable
cyclic
enamides.
Despite
some
advances
made
in
this
realm,
ability
attain
precise
regiocontrol
still
remains
challenging,
especially
endo
cyclization
that
leads
six-membered
and
larger
azacyclic
rings.
Herein,
we
report
NiH-catalyzed
intramolecular
of
alkynyl
dioxazolones
allows
an
excellent
selectivity,
thus
affording
range
six-
eight-membered
endocyclic
enamides
with
broad
scope.
Mechanistic
investigations
revealed
Ni(I)
catalysis
is
operative
current
system,
proceeding
via
regioselective
syn-hydronickelation,
alkenylnickel
E/Z
isomerization,
Ni-centered
inner-sphere
nitrenoid
transfer.
In
particular,
key
isomerization
step,
which
previously
lacked
mechanistic
understandings,
was
found
take
place
through
η2-vinyl
transition
state.
The
synthetic
value
protocol
demonstrated
by
diastereoselective
modifications
obtained
highly
functionalized
δ-lactam
scaffolds.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(41), С. 18803 - 18809
Опубликована: Окт. 4, 2022
A
method
for
the
regiodivergent
aminooxygenation
of
aryl
olefins
under
electrophotocatalytic
conditions
is
described.
The
procedure
employs
a
trisaminocyclopropenium
(TAC)
ion
catalyst
with
visible
light
irradiation
controlled
electrochemical
potential
to
convert
corresponding
oxazolines
high
chemo-
and
diastereoselectivity.
With
judicious
choice
between
two
inexpensive
abundant
reagents,
namely
water
urethane,
either
2-amino-1-ol
or
1-amino-2-ol
derivatives
could
be
prepared
from
same
substrate.
This
amenable
multigram
synthesis
oxazoline
products
low
loadings.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(14), С. 8150 - 8162
Опубликована: Апрель 4, 2023
Difunctionalization
of
olefins
offers
an
attractive
approach
to
access
complex
chiral
structures.
Reported
herein
is
the
design
N-protected
O-allylhydroxyamines
as
bifunctional
that
undergo
catalytic
asymmetric
1,2-carboamidation
with
three
classes
(hetero)arenes
afford
amino
alcohols
via
C-H
activation.
The
C═C
bond
in
O-allylhydroxyamine
activated
by
intramolecular
electrophilic
amidating
moiety
well
a
migrating
directing
group.
carboamidation
reaction
pattern
depends
on
nature
(hetero)arene
reagent.
Simple
achiral
reacted
give
centrally
β-amino
excellent
enantioselectivity.
employment
axially
prochiral
or
racemic
heteroarenes
afforded
both
axial
and
central
chirality
enantio-
diastereoselectivity.
In
case
heteroarenes,
coupling
follows
kinetic
resolution
s-factor
up
>600.
A
nitrene-based
mechanism
has
been
suggested
based
experimental
studies,
unique
mode
induction
diastereoselectivity
proposed.
Applications
alcohol
products
have
demonstrated.
ACS Catalysis,
Год журнала:
2024,
Номер
14(7), С. 4510 - 4522
Опубликована: Март 12, 2024
Organosilicons
are
privileged
skeletons
in
the
domains
of
pharmaceutical
chemistry,
organic
synthesis,
and
materials
science.
Hence,
investigating
catalytic
techniques
for
synthesis
organosilicon
compounds
has
received
a
great
deal
emphasis.
Carbosilylation
alkenes
is
an
efficient
technique
to
introduce
diverse
molecular
architectures
containing
silicon
into
chemical
space.
However,
organohalides
pseudohalides
prerequisites
most
existing
carbosilylation
protocols.
On
other
hand,
utilization
C–H
activation
been
sowing
seeds
successful
development
intricate
scaffolds.
In
this
regard,
synthetic
accessibility
complexed
derivatives
by
through
meta-C–H
approach
remained
intangible.
Herein,
we
present
three-component
strategy
arylsilylation
olefins
with
(het)arenes
silanes
integrating
iron-catalyzed
silyl
radical
generation,
coupled
intrinsic
reactivity
alkene,
ruthenium-catalyzed
functionalization
(het)arene,
leading
targeted
cross-coupled
carbosilylated
product.
addition,
theoretical
investigations
state-of-the-art
dispersion
corrected
density
functional
theory
at
B3PW91-D3/Def2TZVP/CPCM(PhCF3)
shed
intriguing
insights
on
selectivity
probable
mechanistic
pathway
underexplored
cooperative
3d/4d
transition
metal
catalysis,
such
as
formation
its
addition
alkene
catalyzed
iron,
followed
meta-selective
ruthenium
bound
arene,
furnishing
C4
substituted
(het)arene
functionalized
compounds.
Journal of the American Chemical Society,
Год журнала:
2021,
Номер
143(33), С. 13408 - 13417
Опубликована: Авг. 10, 2021
The
chemo-,
regio-,
diastereo-,
and
enantioselective
1,2-oxyamination
of
alkenes
using
selenium(II/IV)
catalysis
with
a
chiral
diselenide
catalyst
is
reported.
This
method
uses
N-tosylamides
to
generate
oxazoline
products
that
are
useful
both
as
protected
1,2-amino
alcohol
motifs
ligands.
reaction
proceeds
in
good
yields
excellent
enantio-
diastereoselectivity
for
variety
pendant
functional
groups
such
sulfonamides,
alkyl
halides,
glycol-protected
ketones.
Furthermore,
the
rapid
generation
demonstrated
expeditious
assembly
PHOX
ligands
well
diversely
amino
alcohols.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(9), С. 4277 - 4285
Опубликована: Фев. 24, 2022
Catalytic
carbon–nitrogen
bond
formation
in
hydrocarbons
is
an
appealing
synthetic
tool
to
access
valuable
nitrogen-containing
compounds.
Although
a
number
of
approaches
have
been
developed
construct
bifunctional
α-amino
carbonyl
scaffold
this
realm,
installation
amino
functionality
at
the
remote
and
unfunctionalized
aliphatic
sites
remains
underdeveloped.
Here
we
present
tandem
iridium
catalysis
that
enables
redox-relay
amidation
alkenyl
alcohols
via
chain
walking
metal-nitrenoid
transfer,
which
eventually
offers
new
route
various
ketones
with
excellent
regioselectivity.
The
virtue
transformation
unrefined
isomeric
mixture
can
be
utilized
as
readily
available
starting
materials
lead
regioconvergent
amidation.
Mechanistic
investigations
revealed
reaction
proceeds
process
involving
two
key
components
intermolecular
nitrenoid
transfer
assistance
hydrogen
bonding,
thus
representing
competence
Ir
for
olefin
migratory
C–N
coupling
high
efficiency
exquisite
selectivity.
Chemical Science,
Год журнала:
2023,
Номер
14(44), С. 12447 - 12476
Опубликована: Янв. 1, 2023
The
introduction
of
nitrogen
atoms
into
small
molecules
is
fundamental
importance
and
it
vital
that
ever
more
efficient
selective
methods
for
achieving
this
are
developed.
With
aim,
the
potential
nitrene
chemistry
has
long
been
appreciated
but
its
application
constrained
by
extreme
reactivity
these
labile
species.
This
liability
however
can
be
attenuated
complexation
with
a
transition
metal
resulting
nitrenoids
have
unique
highly
versatile
which
includes
amination
certain
types
aliphatic
C-H
bonds
as
well
reactions
alkenes
to
afford
aziridines.
At
least
one
new
chiral
centre
typically
formed
in
processes
development
catalysts
exert
control
over
enantioselectivity
nitrenoid-mediated
become
growing
area
research,
particularly
past
two
decades.
Compared
some
synthetic
methods,
nitrenoid
notable
chemists
draw
from
diverse
array
metals
,
ranging
metal-ligand
complexes,
bearing
variety
ligand
types,
via
bio-inspired
metalloporphyrins,
all
way
through
to,
very
recently,
engineered
enzymes
themselves.
In
latter
category
particular,
rapid
progress
being
made,
rate
suggests
approach
may
instrumental
addressing
outstanding
challenges
field.
review
covers
key
developments
strategies
shaped
field,
addition
latest
advances,
up
until
September
2023.