Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(37)
Published: Aug. 2, 2024
Abstract
A
strategy
for
transition
metal‐free
cross‐coupling
of
alkyl
nitroso‐carbamates
and
boronic
acids
is
reported.
The
N
‐nitroso
carbamates
are
easily
prepared
from
the
corresponding
amine
in
two
simple
steps.
This
method
allows
synthesis
a
wide
variety
secondary
boronates,
benzylic
boronates
formal
Csp
3
−Csp
2
products
under
operationally
conditions.
Functional
group
tolerance
also
demonstrated
applied
modification
lysine
to
make
non‐canonical
amino
acids.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(4), P. 2351 - 2357
Published: Jan. 17, 2024
Cross-coupling
catalysts
typically
react
and
unite
functionally
distinct
partners
via
sequential
inner-sphere
elementary
steps:
coordination,
migratory
insertion,
reductive
elimination,
etc.
Here,
we
report
a
single
catalyst
that
cross-couples
styrenes
benzyl
bromides
iterative
outer-sphere
metal–ligand-carbon
interactions.
Each
partner
forms
stabilized
radical
intermediate,
yet
heterocoupled
products
predominate.
The
system
is
redox-neutral
and,
thus,
avoids
exogenous
oxidants,
resulting
in
simple
scalable
conditions.
Numerous
variations
of
alkene
hydrobenzylation
are
made
possible,
including
access
to
the
privileged
heterodibenzyl
(1,2-diarylethane)
motif
challenging
quaternary
carbon
variants.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(5), P. 3043 - 3051
Published: Jan. 26, 2024
Cross-electrophile
coupling
has
emerged
as
an
attractive
and
efficient
method
for
the
synthesis
of
C(sp2)–C(sp3)
bonds.
These
reactions
are
most
often
catalyzed
by
nickel
complexes
nitrogenous
ligands,
especially
2,2′-bipyridines.
Precise
prediction,
selection,
design
optimal
ligands
remains
challenging,
despite
significant
increases
in
reaction
scope
mechanistic
understanding.
Molecular
parameterization
statistical
modeling
provide
a
path
to
development
improved
bipyridine
that
will
enhance
selectivity
existing
broaden
electrophiles
can
be
coupled.
Herein,
we
describe
generation
computational
ligand
library,
correlation
observed
outcomes
with
features
silico
Ni-catalyzed
cross-electrophile
coupling.
The
new
nitrogen-substituted
display
5-fold
increase
product
formation
versus
homodimerization
when
compared
current
state
art.
This
yield
was
general
several
couplings,
including
challenging
aryl
chloride
N-alkylpyridinium
salt.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(39), P. 21189 - 21196
Published: Sept. 20, 2023
The
coupling
of
carboxylic
acids
and
amines
to
form
amide
linkages
is
the
most
commonly
performed
reaction
in
pharmaceutical
industry.
Herein,
we
report
a
new
strategy
that
merges
these
traditional
partners
generate
sulfonamides,
important
bioisosteres.
This
method
leverages
copper
ligand-to-metal
charge
transfer
(LMCT)
convert
aromatic
sulfonyl
chlorides,
followed
by
one-pot
amination
corresponding
sulfonamide.
process
requires
no
prefunctionalization
native
acid
or
amine
extends
diverse
set
aryl,
heteroaryl,
s-rich
aliphatic
substrates.
Further,
extend
this
synthesis
(hetero)aryl
fluorides,
which
have
found
utility
as
"click"
handles
chemical
probes
programmable
bifunctional
reagents.
Finally,
demonstrate
protocols
analogue
synthesis.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(18), P. 9951 - 9958
Published: May 1, 2023
Carbon-heteroatom
bonds,
most
often
amide
and
ester
are
the
standard
method
to
link
together
two
complex
fragments
because
carboxylic
acids,
amines,
alcohols
ubiquitous
reactions
reliable.
However,
C-N
C-O
linkages
a
metabolic
liability
they
prone
hydrolysis.
While
C(sp
Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: July 3, 2023
High-throughput
experimentation
(HTE)
is
an
increasingly
important
tool
in
reaction
discovery.
While
the
hardware
for
running
HTE
chemical
laboratory
has
evolved
significantly
recent
years,
there
remains
a
need
software
solutions
to
navigate
data-rich
experiments.
Here
we
have
developed
phactor™,
that
facilitates
performance
and
analysis
of
laboratory.
phactor™
allows
experimentalists
rapidly
design
arrays
reactions
or
direct-to-biology
experiments
24,
96,
384,
1,536
wellplates.
Users
can
access
online
reagent
data,
such
as
inventory,
virtually
populate
wells
with
produce
instructions
perform
array
manually,
assistance
liquid
handling
robot.
After
completion
array,
analytical
results
be
uploaded
facile
evaluation,
guide
next
series
All
metadata,
are
stored
machine-readable
formats
readily
translatable
various
software.
We
also
demonstrate
use
discovery
several
chemistries,
including
identification
low
micromolar
inhibitor
SARS-CoV-2
main
protease.
Furthermore,
been
made
available
free
academic
24-
96-well
via
interface.
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
Science,
Journal Year:
2024,
Volume and Issue:
385(6715), P. 1331 - 1337
Published: Sept. 19, 2024
The
myriad
nickel-catalyzed
cross-coupling
reactions
rely
on
the
formation
of
an
organonickel
intermediate,
but
limitations
in
forming
monoalkylnickel
species
have
limited
options
for
C(sp
3
)
cross-coupling.
monoalkylnickel(II)
from
abundant
carboxylic
acid
esters
would
be
valuable,
derivatives
are
primarily
decarboxylated
to
form
alkyl
radicals
that
lack
correct
reactivity.
In
this
work,
we
disclose
a
facile
oxidative
addition
and
decarbonylation
sequence
forms
intermediates
through
nonradical
process.
key
ligand,
bis(4-methylpyrazole)pyridine,
accelerates
decarbonylation,
stabilizes
alkylnickel(II)
destabilizes
off-cycle
nickel(0)
carbonyl
species.
utility
new
reactivity
)-C(sp
bond
is
demonstrated
reaction
challenging
by
purely
radical
methods—the
selective
primary
with
iodides.
Communications Chemistry,
Journal Year:
2024,
Volume and Issue:
7(1)
Published: Feb. 3, 2024
Abstract
Amines
and
carboxylic
acids
are
abundant
chemical
feedstocks
that
nearly
exclusively
united
via
the
amide
coupling
reaction.
The
disproportionate
use
of
leaves
a
large
section
unexplored
reaction
space
between
amines
acids:
two
most
common
building
blocks.
Herein
we
conduct
thorough
exploration
amine–acid
systematic
enumeration
reactions
involving
simple
amine–carboxylic
acid
pair.
This
approach
to
investigates
coarse
fine
modulation
physicochemical
properties
molecular
shapes.
With
invention
methods
becoming
increasingly
automated
bringing
conceptual
into
reality,
our
map
provides
an
entirely
new
axis
for
rational
property
design.
