Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(45)
Опубликована: Авг. 6, 2024
Abstract
α‐Silylalkylamines
and
α‐borylalkylamines
are
versatile
synthetic
intermediates
attractive
scaffolds
found
in
pharmaceutical
drugs
agrochemicals.
Despite
great
progress
on
methods
for
preparation
of
α‐silylalkylamines
or
α‐borylalkylamines,
there
no
general
strategies
α‐boryl‐α‐silylalkylamines
the
reactivity
has
not
been
explored.
Here
we
report
deoxygenative
geminal
silylboration
amides
using
silylboronates
presence
alkoxide
base
catalyst,
producing
α‐boryl‐α‐silylalkylamines.
The
silicon
boron
groups
to
be
utilized
chemoselective
transformations,
such
as
protonation
alkylation.
This
protocol
serves
various
from
readily
available
amides.
ACS Catalysis,
Год журнала:
2024,
Номер
14(3), С. 1725 - 1732
Опубликована: Янв. 18, 2024
The
development
of
a
general
and
selective
method
for
α-C(sp3)–H
silylation
feedstock
amines
has
been
long-standing
challenge.
In
this
paper,
we
disclose
mild,
general,
practical,
highly
regio-
diastereoselective
various
readily
available
acyclic,
cyclic,
aromatic
with
silylboranes
through
copper-catalyzed
intramolecular
1,5-hydrogen
atom
transfer
(HAT)
strategy.
mild
activation
2-iodobenzamide
to
generate
an
aryl
radical
enabled
by
ligand-coordinated
silyl
copper
complex
without
additional
heating
or
photoinduced
conditions,
as
well
the
1,5-HAT
process
produce
crucial
α-aminoalkyl
species,
is
key
success
chemistry.
This
protocol
demonstrated
its
potential
utility
in
late-stage
modification
structurally
drugs
bioactive
molecules.
Therefore,
it
expected
that
will
find
applications
synthetic
chemistry
drug
discovery.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(28), С. 19286 - 19294
Опубликована: Июль 3, 2024
As
one
of
the
most
powerful
trifluoromethylation
reagents,
(trifluoromethyl)trimethylsilane
(TMSCF3)
has
been
widely
used
for
synthesis
fluorine-containing
molecules.
However,
to
best
our
knowledge,
simultaneous
incorporation
both
TMS-
and
CF3-
groups
this
reagent
onto
same
carbon
products
not
realized.
Herein,
we
report
an
unprecedented
SmI2/Sm
promoted
deoxygenative
difunctionalization
amides
with
TMSCF3,
in
which
silyl
trifluoromethyl
are
incorporated
into
final
product,
yielding
α-silyl-α-trifluoromethyl
amines
high
efficiency.
Notably,
group
could
be
further
transformed
other
functional
groups,
providing
a
new
method
α-quaternary
α-CF3-amines.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(12), С. 7956 - 7962
Опубликована: Март 12, 2024
Enantioenriched
2-azabicyclo[3.1.0]hexanes
are
accessed
from
readily
available
allyl
substituted
α-isocyanoesters
by
intramolecular
(1
+
2)
cycloaddition
with
the
olefinic
moiety
and
isocyano
carbon
as
respective
C2
C1
units.
Cyclopropanation
is
initiated
1,1-hydrocupration
of
isocyanide
followed
formimidoylcopper
to
copper
α-aminocarbenoid
equilibration
subsequent
cycloaddition.
The
unprecedented
copper/chiral
phosphoric
acid
(CPA)
catalytic
system
can
be
operated
in
presence
water
under
air,
delivering
a
variety
containing
an
angular
all-carbon
quaternary
stereocenter
good
excellent
yields
enantioselectivity.
Organic Letters,
Год журнала:
2024,
Номер
26(12), С. 2483 - 2488
Опубликована: Март 15, 2024
An
enantioselective
deoxygenative
functionalization
of
secondary
amides
with
vinylpridines
is
developed
by
merging
relay
iridium
catalysis
and
cooperative
photoredox-chiral
Brønsted
acid
catalysis,
affording
a
series
valuable
chiral
amines
in
moderate
to
good
yields
enantioselectivities.
The
intriguing
multiple
catalytic
system
invoking
triple-catalysis
was
found
be
the
key
success
current
reactions,
which
may
stimulate
further
development
methodologies
for
asymmetric
transformations
amides.
Green Chemistry,
Год журнала:
2023,
Номер
25(22), С. 9080 - 9085
Опубликована: Янв. 1, 2023
A
deoxygenative
arylation
of
amides
using
aromatic
nitriles
via
merging
Ir-catalyzed
amide
reduction
with
electrochemistry
has
been
achieved,
which
may
provide
an
alternative
strategy
for
access
to
value-added
amines
from
inert
amides.
ACS Catalysis,
Год журнала:
2024,
Номер
14(11), С. 8865 - 8873
Опубликована: Май 23, 2024
α-Amino
silanes
and
their
derivatives
play
pivotal
roles
across
diverse
applications,
yet
current
synthetic
methods
often
entail
intricate
functional
group
manipulations.
Despite
the
widespread
use
of
allyl
as
carbon
nucleophiles
in
organic
synthesis,
participation
allylic
C–H
functionalization
has
been
underexplored.
Herein,
we
unveil
a
metal-free
intermolecular
amination
facilitated
by
β-silicon
effect.
This
protocol
yields
α-amino
with
exceptional
site
selectivity.
Notably,
wide
array
secondary
tertiary
are
synthesized
high
without
desilylation,
owing
to
mild
reaction
conditions
pathway.
Mechanistic
elucidations
highlight
activation
effect
silyl
moiety
on
alkenes,
alongside
its
stabilizing
influence
adjacent
developing
positive
charges,
which
selectively
drives
closed
transition
state,
ensuring
Chemical Communications,
Год журнала:
2024,
Номер
60(64), С. 8454 - 8457
Опубликована: Янв. 1, 2024
A
novel
deoxygenative
alkynylation
of
amides
promoted
by
a
synergistic
action
divalent
rare-earth
element
and
transition
metal
has
been
developed.
In
this
method,
α-alkynyl
substituted
amines
are
synthesized
from
unactivated
alkynes
in
single
transformation.
Broad
substrate
scope
excellent
selectivity
for
CO
cleavage
demonstrated.
This
approach
represents
general
method
the
construction
versatile
amide
bonds.
Chinese Journal of Organic Chemistry,
Год журнала:
2023,
Номер
43(5), С. 1857 - 1857
Опубликована: Янв. 1, 2023
A
direct
deoxygenative
silylation
of
amides
with
silylboronate
reagents
is
developed
in
the
presence
SmI2/Mg,
affording
a
variety
high
value-added
α-aminosilane
compounds
moderate
to
excellent
yields
good
functional
group
compatibility.The
key
success
this
strategy
lies
merging
activation
induced
by
electron
transfer
1,2-metalate
migration.The
addition
Xantphos
ligand
can
improve
reaction
efficiency.The
reactions
are
operationally
simple
and
proceed
under
mild
conditions,
raw
materials
easily
available
products
highly
valuable.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(45)
Опубликована: Авг. 6, 2024
Abstract
α‐Silylalkylamines
and
α‐borylalkylamines
are
versatile
synthetic
intermediates
attractive
scaffolds
found
in
pharmaceutical
drugs
agrochemicals.
Despite
great
progress
on
methods
for
preparation
of
α‐silylalkylamines
or
α‐borylalkylamines,
there
no
general
strategies
α‐boryl‐α‐silylalkylamines
the
reactivity
has
not
been
explored.
Here
we
report
deoxygenative
geminal
silylboration
amides
using
silylboronates
presence
alkoxide
base
catalyst,
producing
α‐boryl‐α‐silylalkylamines.
The
silicon
boron
groups
to
be
utilized
chemoselective
transformations,
such
as
protonation
alkylation.
This
protocol
serves
various
from
readily
available
amides.
