Advanced Science,
Journal Year:
2023,
Volume and Issue:
11(9)
Published: Dec. 15, 2023
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.
Chemical Communications,
Journal Year:
2023,
Volume and Issue:
59(15), P. 2118 - 2121
Published: Jan. 1, 2023
A
Cu(OTf)
2
-mediated
regioselective
dearomative
aryl-hydroxylation
across
the
C(sp
)N
bond
of
2-aryl
quinoxalines
and
bis-
N
-arylation
(benz)imidazoles
were
developed
using
aryl
boronic
acids.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(50), P. 27254 - 27261
Published: Dec. 11, 2023
Alkene
borylfunctionalization
reactions
have
emerged
as
useful
methods
for
chemical
synthesis.
While
much
progress
has
been
made
on
1,2-borylamination
reactions,
the
related
1,1-
and
1,3-borylaminations
not
reported.
Herein,
a
Ni-catalyzed
1,1-borylamination
of
1,1-disubstituted
monosubstituted
alkenes
1,3-borylamination
cyclic
are
presented.
Key
to
development
these
was
identification
an
alkyllithium
activator
in
combination
with
Mg
salts.
The
utility
products
mechanistic
details
discussed.
Physical Chemistry Chemical Physics,
Journal Year:
2024,
Volume and Issue:
26(15), P. 12162 - 12167
Published: Jan. 1, 2024
The
aromaticity
pattern
of
azulene
has
been
reexamined
through
the
magnetic
and
delocalization
criteria,
results
indicate
that
is
governed
by
Glidewell–Lloyd
rule.
Organic Chemistry Frontiers,
Journal Year:
2022,
Volume and Issue:
9(22), P. 6165 - 6171
Published: Jan. 1, 2022
An
efficient
intermolecular
C2,3-H
aminoalkylation
of
indoles
with
9
H
-xanthenes
and
azoles
via
iron–iodine
co-catalyzed
tandem
C–N/C–C
bond
formation
has
been
developed.
The Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
88(3), P. 1844 - 1854
Published: Jan. 25, 2023
The
alkene-based
o-[1-(p-MeO-phenyl)vinyl]benzoates
(PMPVB)
donors
that
can
be
remotely
activated
under
catalytic
Brønsted
acidic
conditions
have
been
utilized
to
synthesize
the
C-linked
indolyl
glycosides
in
a
regio-
and
stereoselective
manner.
highly
reactive
glycosyl
allow
usage
of
poorly
nucleophilic
N-Boc
N-acetyl
indole
derivatives,
leading
excellent
yields
stereoselectivities.
Also,
were
developed
for
recycling
byproduct,
which
significantly
improves
potential
these
donors.
Chemical Science,
Journal Year:
2023,
Volume and Issue:
14(9), P. 2342 - 2347
Published: Jan. 1, 2023
Catalyzed
by
CuCl
and
DPEphos,
various
β-polyfluoroaryl
boronates
were
obtained
from
styrenes
polyfluoroarenes
via
defluorinative
arylboration.
With
the
use
of
a
chiral
ligand,
first
example
version
was
realized.
Chinese Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
43(4), P. 1271 - 1271
Published: Jan. 1, 2023
Indolines
are
prevalent
scaffolds
of
numerous
natural
products,
pharmaceutical
agents,
and
bioactive
molecules,
therefore,
various
strategies
have
been
developed
to
access
indolines.Indole
dearomatization
has
recognized
as
an
important
straightforward
strategy
for
constructing
diverse
functionalized
indolines.Among
a
multitude
indoles
dearomatization,
the
well-known
relied
on
inherent
nucleophilicity
indole,
while
migratory
insertion
widely
applied
in
recent
years.Herein,
advances
Pd,
Ni,
Co,
Cu-catalyzed
tandem
dearomatizations
via
radical-mediated
process
summarized
detailedly,
mechanism
development
tendency
this
reactions
discussed.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(12), P. 2359 - 2364
Published: March 15, 2024
A
palladium-catalyzed
dearomative
diarylation
of
C2-deuterated
or
C2-nonsubstituted
indoles
through
domino
Heck/Suzuki
coupling
is
established.
Relying
on
electron-deficient
phosphite
ligand,
side
reactions
including
intermolecular
Suzuki
and
intramolecular
C–D/H
arylation
are
inhibited
a
wide
range
2,3-diarylated
indolines
bearing
vicinal
tertiary
stereocenters
deuterated
ones
afforded
in
moderate
to
excellent
yields
(up
94%)
diastereoselectivities
(>20:1).
The
catalyst
loading
can
be
lowered
0.02
mol
%
at
elevated
temperature.
