Angewandte Chemie,
Journal Year:
2023,
Volume and Issue:
135(23)
Published: March 29, 2023
Abstract
Despite
the
widespread
success
in
functionalization
of
C(sp
2
)−H
bonds,
deliberate
3
bonds
a
highly
site‐
and
stereoselective
manner
remains
longstanding
challenge.
Herein,
we
report
an
iridium/aluminum
cooperative
catalytic
system
that
enables
β‐selective
C−H
borylation
saturated
cyclic
amines
lactams.
Furthermore,
have
accomplished
enantioselective
variant
using
binaphthol‐derived
chiral
aluminum
catalysts
to
forge
C−B
with
high
levels
stereocontrol.
Computational
studies
suggest
formation
Lewis
pair
substrates
is
crucial
lower
energy
transition
state
for
rate‐determining
reductive
elimination
step.
Chemical Science,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
A
titanium-catalyzed
reductive
cyclization
of
vinyl
boronates
with
gem
-dihaloalkanes
is
developed.
α-Substituted
cyclic
that
are
otherwise
difficult
to
access,
such
as
those
heteroatom-containing
rings,
readily
obtained.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(9), P. 3249 - 3254
Published: Jan. 1, 2024
A
one-step
approach
to
borylated
cyclobutanes
from
amides
of
carboxylic
acids
and
vinyl
boronates
is
elaborated.
The
reaction
proceeds
via
the
thermal
[2
+
2]-cycloaddition
in
situ
-generated
keteniminium
salts.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Jan. 1, 2024
Cooperative
NHC/photoredox
catalyzed
deconstruction–reconstruction
of
aryl
cyclopropanes
was
described
to
access
various
α-acylated
cyclopropane
derivatives.
Chemical Science,
Journal Year:
2023,
Volume and Issue:
14(31), P. 8355 - 8359
Published: Jan. 1, 2023
Cycloaddition
is
a
fundamental
transformation,
featuring
the
assembly
of
complex
cyclic
molecules
with
multiple
stereocenters.
We
report
here
silver-catalyzed
[3+2]-cycloaddition
2,3-disubstituted
cyclobutenones
an
array
azomethine
ylide
precursors
iminoesters,
furnishing
azabicycles
in
good
yields
and
enantioselectivities.
Up
to
three
contiguous
all-carbon
quaternary
centers,
including
two
angular
stereocenters,
could
be
constructed
efficiently,
due
high
reactivity
strained
cyclobutenones.
Subsequent
skeletal
remodeling
provided
versatile
distinct
structural
characters.
ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
14(1), P. 124 - 130
Published: Dec. 11, 2023
Catalyst-controlled
C–H
functionalization
using
donor/acceptor
carbenes
has
been
shown
to
be
an
efficient
process
capable
of
high
levels
site
control
and
stereocontrol.
This
study
demonstrated
that
the
scope
carbene
can
extended
systems
where
acceptor
group
is
a
phosphonate.
When
optimized
dirhodium
catalyst,
Rh2(S-di-(4-Br)TPPTTL)4,
((aryl)(diazo)methyl)phosphonates
undergo
highly
enantioselective
(84–99%
ee)
site-selective
(>30:1
r.r.)
benzylic
functionalization.
The
phosphonate
much
more
sterically
demanding
than
previously
studied
carboxylate
ester
group,
leading
higher
selectivity
for
primary
versus
crowded
positions.
effectiveness
this
methodology
by
late-stage
estrone,
adapalene,
(S)-naproxen,
clofibrate,
gemfibrozil
derivatives.
ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
14(1), P. 176 - 182
Published: Dec. 12, 2023
A
highly
enantio-
and
diastereoselective
copper-catalyzed
conjugate
monoborylation
of
γ,γ-disubstituted
cyclohexadienone
derivatives
is
reported.
Two
contiguous
stereocenters
are
generated
in
this
group-selective
reaction,
one
at
the
formed
boron-bearing
carbon
atom
a
neopentylic
position
quaternary
atom.
subsequent
1,4-addition
boron
nucleophile
to
remaining
α,β-unsaturated
acceptor
allows
for
construction
another
stereocenter
other
position,
thereby
leading
three
adjacent
stereogenic
atoms
congested
environment.
The
diastereoselectivity
that
second
borylation
can
be
controlled
by
different
chiral
ligands
selectively
afford
either
syn-
or
anti-1,3-diborylated
product.
Catalysis Science & Technology,
Journal Year:
2024,
Volume and Issue:
14(19), P. 5488 - 5504
Published: Jan. 1, 2024
Organoborons
play
a
crucial
role
in
organic
synthesis,
easing
the
construction
of
C–C
and
C–X
bonds,
which
turn
sensitize
C(sp
3
)–H
borylation
reactions.
