Angewandte Chemie,
Journal Year:
2023,
Volume and Issue:
135(25)
Published: April 22, 2023
Abstract
We
report
that
a
nickel
catalyst
system
with
modified
1,1′‐spirobiindane‐7,7′‐diol‐phosphoramidite
(SPINOL)
as
the
chiral
ligand
can
enable
coupling
of
tertiary
cyclobutenols
and
arylboroxines
in
an
enantioconvergent
manner,
providing
cyclobutenes
all‐carbon
quaternary
stereocenter
good
yields
(up
to
84
%
yield)
excellent
enantioselectivities
>99
ee).
Moreover,
catalytic
be
applied
kinetic
resolution
under
slightly
conditions,
giving
enantioenriched
s
factor
up
>200.
The
reaction
uses
free
hydroxyl
groups
leaving
group
without
additional
activation
while
strained
ring
remains
untouched.
Preliminary
mechanistic
studies
reveal
inherent
discrepant
reactivity
two
enantiomers
is
key
controllable
process.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(28), P. 5220 - 5225
Published: July 12, 2023
An
efficient
palladium-catalyzed
2-fluoroallylation
of
P(O)H
compounds
with
gem-difluorocyclopropanes
is
presented.
The
reaction
provides
a
variety
2-fluoroallylic
phosphorus
in
good
yields
high
Z
selectivity
through
the
sequential
C-C
bond
activation,
C-F
cleavage,
and
C-P
coupling
process.
Various
H-phosphonates,
H-phosphinates,
secondary
phosphine
oxides
are
all
tolerated.
In
addition,
gram-scale
synthesis
late-stage
modification
complex
bioactive
molecules
show
practical
utilities
transformation.
Advanced Science,
Journal Year:
2024,
Volume and Issue:
11(18)
Published: March 9, 2024
Abstract
Transition‐metal
(TM)
catalyzed
reaction
of
gem
‐difluorinated
cyclopropanes
(
‐DFCPs)
has
drawn
much
attention
recently.
The
generally
occurs
via
the
activation
distal
C─C
bond
in
‐DFCPs
by
a
low‐valent
TM
through
oxidative
addition,
eventually
producing
mono‐fluoro
olefins
as
coupling
products.
However,
achieving
regioselective
proximal
that
overcomes
intrinsic
reactivity
catalysis
remains
elusive.
Here,
new
mode
enabled
high‐valent
copper
catalysis,
which
allows
exclusive
congested
is
presented.
achieves
fluoroarylation
uses
NFSI
(N‐fluorobenzenesulfonimide)
electrophilic
fluoro
reagent
and
arenes
C─H
nucleophiles,
enabling
synthesis
diverse
CF
3
‐containing
scaffolds.
It
proposed
species
plays
an
important
role
possibly
σ‐bond
metathesis.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(25)
Published: April 22, 2023
We
report
that
a
nickel
catalyst
system
with
modified
1,1'-spirobiindane-7,7'-diol-phosphoramidite
(SPINOL)
as
the
chiral
ligand
can
enable
coupling
of
tertiary
cyclobutenols
and
arylboroxines
in
an
enantioconvergent
manner,
providing
cyclobutenes
all-carbon
quaternary
stereocenter
good
yields
(up
to
84
%
yield)
excellent
enantioselectivities
>99
ee).
Moreover,
catalytic
be
applied
kinetic
resolution
under
slightly
conditions,
giving
enantioenriched
s
factor
up
>200.
The
reaction
uses
free
hydroxyl
groups
leaving
group
without
additional
activation
while
strained
ring
remains
untouched.
Preliminary
mechanistic
studies
reveal
inherent
discrepant
reactivity
two
enantiomers
is
key
controllable
process.
Organic Process Research & Development,
Journal Year:
2024,
Volume and Issue:
28(4), P. 937 - 948
Published: March 21, 2024
Significant
emphasis
has
been
placed
on
the
development
of
nonprecious
metal
alternatives
to
precious-metal-catalyzed
reactions
due
lower
cost
and
greater
sustainability
they
can
achieve.
This
review
is
part
a
series
describing
advances
in
nonprecious-metal-catalyzed
transformations
published
between
March
June
2023
that
are
relevant
pharmaceutical
process
chemistry.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Sept. 18, 2024
Herein,
we
reported
a
copper(0)-catalyzed
reductive
coupling
of
disulfurating
reagents
and
(hetero)aryl/alkyl
halides.
Copper(0)
can
be
directly
inserted
into
tetrasulfide
then
undergoes
with
(hetero)aryl
Iodides
to
construct
disulfide.
The
method
features
the
unprecedented
use
(tetrasulfides)
in
cross-coupling
chemistry
is
convenient
broad
substrate
scopes,
even
applicable
different
halogenated
hydrocarbons.
It
worth
noting
that
methodology
practical
late-stage
modification
bioactive
scaffolds
pharmaceuticals.
In
meantime,
synthesis
disulfides
successfully
achieved
on
gram
scale,
indicating
approach
highly
valuable.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(22), P. 6311 - 6318
Published: Jan. 1, 2024
Co-catalyzed
asymmetric
reductive
addition
of
ketimine
with
cyclopropyl
chloride
has
been
realized
to
access
diverse
chiral
amino
esters
bearing
fragments
broad
functional
group
tolerance
and
excellent
enantioselectivities.
Synthesis,
Journal Year:
2023,
Volume and Issue:
56(08), P. 1244 - 1258
Published: Nov. 2, 2023
Abstract
Catalytic
Sonogashira
cross-coupling
reactions
represent
an
efficient
and
versatile
approach
for
constructing
complex
alkynes
from
readily
available
starting
materials.
Despite
notable
progress
in
this
field,
the
development
of
transition-metal-catalyzed
alkyl
electrophiles
remains
limited.
This
limitation
primarily
stems
low
reactivity
pronounced
propensity
these
compounds
towards
β-H
elimination.
To
overcome
challenges,
researchers
have
investigated
use
palladium,
nickel,
copper
catalysts
electrophiles.
Furthermore,
significant
strides
been
made
achieving
asymmetric
short
review
provides
overview
recent
breakthroughs
area.
1
Introduction
2
Palladium-Catalyzed
Cross-Coupling
Alkyl
Halides
3
Nickel-Catalyzed
4
Copper-Catalyzed
Electrophiles
4.1
Racemic
4.2
Copper-catalyzed
Asymmetric
5
Conclusions
Perspectives
Chemistry - An Asian Journal,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 18, 2024
Abstract
A
photopromoted
Pd‐catalyzed
Heck
reaction
of
gem
‐difluorocyclopropyl
bromides
(DFCBs)
with
styrenes
to
deliver
vinyl
‐difluorinated
cyclopropanes
(VDFCs)
under
mild
conditions
has
been
developed.
The
demonstrates
good
functional
group
compatibility
while
providing
high
E/Z
ratio
the
products.
Furthermore,
desired
VDFCs
can
be
easily
transformed
into
fluorinated
cyclic/acyclic
architectures,
which
may
broaden
its
applications
in
organic
synthesis.
