ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
14(1), P. 547 - 553
Published: Dec. 26, 2023
Direct
transformations
of
readily
available
amines
or
amides
via
C–H
bond
functionalization
could
provide
a
fast
route
for
accessing
complex
molecules.
While
various
groups
have
been
successfully
incorporated
into
the
α
position
nitrogen
atom
with
photoredox
system
activation,
couplings
functionalized
alkyl
halides
are
still
very
challenging.
Herein,
we
report
direct
and
convenient
protocol
β-amino
boronates
through
C(sp3)–C(sp3)
coupling
α-bromoboronates.
The
mild
conditions
allow
good
functional
group
tolerance
broad
scope.
application
method
in
late-stage
modification
molecules
further
demonstrates
its
great
potential
organic
synthesis.
Mechanistic
studies
were
also
conducted,
catalytic
cycle
is
proposed.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(21), P. 11518 - 11523
Published: May 16, 2023
The
first
examples
of
enantioselective
doubly
decarboxylative
cross
coupling
are
disclosed.
Malonate
half
amides
smoothly
coupled
to
a
variety
primary
carboxylic
acids
after
formation
the
corresponding
redox-active
esters
under
Ni-electrocatalytic
conditions
using
new
chiral
ligand
based
on
PyBox,
resulting
in
with
α-alkylated
stereocenters.
scope
reaction
is
broad,
tolerating
numerous
functional
groups,
and
uniformly
proceeds
high
ee.
Finally,
potential
utility
this
radical–radical
reductive
simplify
synthesis
demonstrated
case
studies.
Chemical Reviews,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 26, 2024
Cross-electrophile
coupling
(XEC),
defined
by
us
as
the
cross-coupling
of
two
different
σ-electrophiles
that
is
driven
catalyst
reduction,
has
seen
rapid
progression
in
recent
years.
As
such,
this
review
aims
to
summarize
field
from
its
beginnings
up
until
mid-2023
and
provide
comprehensive
coverage
on
synthetic
methods
current
state
mechanistic
understanding.
Chapters
are
split
type
bond
formed,
which
include
C(sp
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(25), P. 13603 - 13614
Published: June 6, 2023
Chiral
boronic
esters
are
a
class
of
versatile
building
blocks.
We
describe
herein
an
asymmetric
nickel-catalyzed
borylative
coupling
terminal
alkenes
with
nonactivated
alkyl
halides.
The
success
this
reaction
is
ascribed
to
the
application
chiral
anionic
bisoxazoline
ligand.
This
study
provides
three-component
strategy
access
α-
and
β-stereogenic
from
easily
accessible
starting
materials.
protocol
characterized
by
mild
conditions,
wide
substrate
scope
high
regio-
enantioselectivity.
also
showcase
value
method
in
simplifying
synthesis
several
drug
molecules.
Mechanistic
studies
suggest
that
generation
enantioenriched
bearing
α-stereogenic
center
results
stereoconvergent
process,
while
enantioselectivity-controlling
step
β-stereocenter
switched
olefin
migratory
insertion
due
coordination
ester
group.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
63(3)
Published: Dec. 8, 2023
Abstract
The
development
of
boron
reagents
is
crucial
for
synthetic
chemistry.
Herein,
we
present
a
scalable
and
practical
synthesis
diborodichloromethane
(DBDCM)
through
the
reaction
trichloromethyllithium
with
bis(pinacolato)diboron
(B
2
pin
).
resulting
DBDCM
reagent
serves
as
basic
unit
construction
various
structurally
diverse
gem
‐diborylalkanes
controllable
C−Cl
functionalizations.
Moreover,
have
developed
consecutive
tetra‐functionalizations
tertiary
quaternary
carbon
containing
molecules.
use
isotopically
enriched
13
C‐chloroform
10
B
enables
C‐DBDCM
B‐DBDCM
reagents,
which
are
beneficial
convenient
carbon‐13
boron‐10
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(7), P. 4395 - 4406
Published: March 8, 2024
Asymmetric
reductive
three-component
arylalkylation
of
alkenes
via
the
radical
relay
method
has
been
well
established,
while
asymmetric
migratory
insertion
strategy
remains
unexplored.
We
report
enantioselective
nickel-catalyzed
cross-electrophile
with
aryl-
and
alkyl
halides
an
integrated
Heck
carbometalation/radical
cross-coupling
sequence.
This
protocol
employing
a
chiral
Ni/PHOX
catalytic
system
allows
terminal
internal
to
successfully
engage
exquisite
control
regio-,
chemo-,
stereoselectivity.
More
importantly,
this
undergoes
regio-
arylnickelation
followed
by
Csp3–Csp3
elimination,
thus
exhibiting
reverse
regioselectivity
method.
Mild
reaction
conditions
exceptional
functional
group
tolerance
facilitate
method's
compatibility
bioactive
motifs
modular
synthesis
biologically
active
compounds.
The
experiments
density
theory
calculations
provide
insights
into
mechanism
origin
stereoselectivity,
hemilabile
nature
PHOX
ligand
is
critical
for
achieving
arylalkylation.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(18)
Published: March 6, 2024
Geminal
bis(boronates)
are
versatile
synthetic
building
blocks
in
organic
chemistry.
The
fact
that
they
predominantly
serve
as
nucleophiles
the
previous
reports,
however,
has
restrained
their
potential.
Herein
we
disclose
ambiphilic
reactivity
of
α-halogenated
geminal
bis(boronates),
which
first
catalytic
utilization
was
accomplished
by
merging
a
formal
Heck
cross-coupling
with
highly
diastereoselective
allylboration
aldehydes
or
imines,
providing
new
avenue
for
rapid
assembly
polyfunctionalized
boron-containing
compounds.
We
demonstrated
this
cascade
reaction
is
efficient
and
compatible
various
functional
groups,
wide
range
heterocycles.
In
contrast
to
classical
Pd(0/II)
scenario,
mechanistic
experiments
DFT
calculations
have
provided
strong
evidence
cycle
involving
Pd(I)/diboryl
carbon
radical
intermediates.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(28)
Published: April 15, 2024
With
halogen-atom
transfer
as
an
effective
tool,
a
novel
catalytic
enantioselective
protocol
to
generate
chiral
trifluoromethylated
alkynes
has
been
established
by
cooperative
photoredox
and
nickel
catalysis
system,
providing
straightforward
modular
route
access
this
type
of
product
in
good
yields
enantioselectivities.
The
process
is
essential
for
the
reaction
strategy
offers
another
promising
way
utilize
alkyl
halides
with
highly
negative
reduction
potentials.
It
firstly
expands
nickel-catalyzed
asymmetric
reductive
cross-couplings
organohalides
from
traditional
single-electron
transfer.
