2-Aminobiaryls
are
privileged
scaffolds
and
their
cogent
synthesis
diversifications,
particularly
through
the
C-H
bond
activation
strategy,
is
a
continuous
enterprise
in
organic
synthesis.
In
this
realm,
capitalization
on
susceptible
native
amine
(-NH2)
directing
group
beneficial
but
increasingly
challenging
owing
to
its
innate
nucleophilic
reactivity.
Also,
reactions
of
class
substrates
have
traditionally
been
restricted
cross-ring
as
ortho
functionalization
presumably
requires
formation
strained
high-energy
four-membered
metallacycle.
Herein,
we
report
first
example
free
amine-directed
reaction
2-aminobiaryls
under
high-valent
Cp*Co(III)-catalysis,
enabling
regio-
stereoselective
allylation
high
yields.
The
protocol
engages
vinyl
cyclopropanes
allyl
synthons
where
C-C
construction
event
was
tunneled
process
forge
internal
olefin
with
exclusive
(E)-selectivity.
products
were
judicially
used
access
high-value
benzo[d]isoxazoles
dihydro
phenanthridine
derivatives.
Mechanistic
experiments
DFT
calculations
also
conducted
unravel
rationale
behind
unique
site
selectivity,
thermodynamic
constraints
corresponding
intermediates
favoring
over
functionalization.
Data
science
is
assuming
a
pivotal
role
in
guiding
reaction
optimization
and
streamlining
experimental
workloads
the
evolving
landscape
of
synthetic
chemistry.
A
discipline-wide
goal
development
workflows
that
integrate
computational
chemistry
data
tools
with
high-throughput
experimentation
as
it
provides
experimentalists
ability
to
maximize
success
expensive
campaigns.
Here,
we
report
an
end-to-end
data-driven
process
effectively
predict
how
structural
features
coupling
partners
ligands
affect
Cu-catalyzed
C–N
reactions.
The
established
workflow
underscores
limitations
posed
by
substrates
while
also
providing
systematic
ligand
prediction
tool
uses
probability
assess
when
will
be
successful.
This
platform
strategically
designed
confront
intrinsic
unpredictability
frequently
encountered
deployment.
RSC Advances,
Год журнала:
2025,
Номер
15(2), С. 1134 - 1151
Опубликована: Янв. 1, 2025
Due
to
the
presence
of
pyridyl
directing
group,
N-aryl-2-aminopyridines
can
quickly
form
stable
complexes
with
metals,
leading
cyclization
and
functionalization
reactions.
A
large
number
N-heterocycles
nitrogen-based
molecules
be
easily
constructed
via
this
direct
atom-economical
cross-coupling
strategy.
In
review,
we
have
highlighted
transformations
in
various
transition
metal
catalysts,
such
as
palladium,
rhodium,
iridium,
ruthenium,
cobalt
copper.
Organic Letters,
Год журнала:
2024,
Номер
26(8), С. 1672 - 1676
Опубликована: Фев. 15, 2024
The
(3
+
2)
cycloaddition/sulfur
rearrangement
reaction
of
donor–acceptor
cyclopropanes
bearing
a
single
keto
acceptor
with
indoline-2-thiones
has
been
realized.
Under
the
catalysis
Sn(OTf)2,
series
functionalized
3-indolyl-4,5-dihydrothiophenes
were
synthesized
moderate
to
excellent
yields.
Organic Letters,
Год журнала:
2023,
Номер
25(21), С. 3853 - 3858
Опубликована: Май 18, 2023
An
efficient
synthesis
of
benzo[c]phenanthridine
alkaloids
via
a
synergistic
combination
C-C
bond
formation
and
cycloaromatization
reaction
is
described.
Aryl
nitrones
react
with
7-azabenzonorbornadienes
in
the
presence
Rh(III)
catalyst,
providing
pharmaceutically
useful
derivatives
good
to
moderate
yields.
Using
this
methodology,
highly
such
as
norfagaronine,
norchelerythrine,
decarine,
norsanguinarine,
nornitidine
were
prepared
single
step.
Organic & Biomolecular Chemistry,
Год журнала:
2023,
Номер
21(31), С. 6312 - 6316
Опубликована: Янв. 1, 2023
A
series
of
indolylthio-functionalized
ketones
were
constructed
via
a
ring-opening
reaction,
and
the
linear
could
be
further
transformed
into
dihydro-2
H
-thiepino[2,3-
b
]indoles.
ACS Catalysis,
Год журнала:
2023,
Номер
13(19), С. 12543 - 12552
Опубликована: Сен. 11, 2023
2-Aminobiaryls
are
privileged
scaffolds,
and
their
cogent
synthesis
diversifications,
particularly
through
the
C–H
bond
activation
strategy,
a
continuous
enterprise
in
organic
synthesis.
In
this
realm,
capitalizing
on
susceptible
native
amine
(−NH2)
directing
group
is
beneficial
but
increasingly
challenging
owing
to
its
innate
nucleophilic
reactivity.
Additionally,
reactions
of
class
substrates
have
traditionally
been
restricted
cross-ring
bond,
as
ortho-C–H
functionalization
presumably
requires
formation
strained
high-energy
four-membered
metallacycle.
Herein,
we
report
free-amine-directed
reaction
2-aminobiaryls
under
high-valent
Cp*Co(III)-catalysis,
enabling
regio-
stereoselective
allylation
high
yields.
The
protocol
engages
vinyl
cyclopropanes
allyl
synthons,
where
C–C
construction
event
tunneled
process
forge
an
internal
olefin
with
exclusive
(E)-selectivity.
products
were
judicially
used
access
high-value
benzo[d]isoxazoles
dihydrophenanthridine
derivatives.
Mechanistic
experiments
DFT
calculations
also
conducted
unravel
rationale
behind
unique
site
selectivity,
thermodynamic
constraints
corresponding
intermediates
favor
over
functionalization.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(8), С. 5764 - 5777
Опубликована: Апрель 5, 2024
The
Rh(III)-catalyzed
reaction
of
aromatic
ketoximes
with
2-vinylaziridines
affords
ortho-allylation
products
the
phenyl
rings
in
moderate
to
excellent
yields.
requires
0.5
equiv
NaOAc
as
a
base
and
occurs
under
mild
conditions.
protocol
exhibits
ortho-monoallylation
selectivity,
wide
scope
substrates,
good
compatibility
functional
groups.
The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
88(23), С. 16076 - 16090
Опубликована: Ноя. 16, 2023
The
ruthenium-catalyzed
reaction
of
aryl
methyl
thioethers
with
vinylaziridines
affords
ortho-position
mono-
or
bis-allylation
products
depending
on
substituents
the
phenyl
rings
sulfide
substrates
ratio
reactants.
also
features
mild
conditions,
good
product
yields,
wide
scope
substrates,
compatibility
functional
groups,
and
selective
formation
E-configurated
C-C
double
bonds.
Chemical Communications,
Год журнала:
2024,
Номер
60(43), С. 5630 - 5633
Опубликована: Янв. 1, 2024
Substrate-controlled
product
divergence
is
demonstrated
in
Pd-catalyzed
reaction
of
2-aminopyrimidines.
Remote
C5–H
polyfluoroarylation
occurs
with
N
-alkylpyrimidine-2-amines,
while
N–H
dominant
for
-aryl-pyrimidine-2-amines.
