Chinese Journal of Chemistry,
Год журнала:
2023,
Номер
41(24), С. 3593 - 3597
Опубликована: Сен. 10, 2023
Comprehensive
Summary
Aldehydes
are
a
kind
of
important
synthons
and
reagents
in
organic
synthesis.
The
efforts
on
transformations
aldehydes
highly
rewarding
have
always
attracted
considerable
attention.
Herein,
cross‐coupling
with
α‐haloboronates
has
been
achieved
under
dual
nickel/photoredox
catalysis
system.
Considering
the
can
be
easily
obtained
from
our
deoxygenative
difunctionalization
carbonyls
(DODC)
strategy,
this
protocol
provides
formal
to
one‐carbon‐prolonged
ketone
products.
mild
conditions
enabled
good
functional
group
tolerance
broad
substrate
applicability.
application
method
was
presented
via
tunable
synthesis
two
ketones
very
similar
skeletons
same
aldehydes.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(4), С. 2081 - 2087
Опубликована: Янв. 23, 2023
Substantial
advances
in
enantioconvergent
C(sp3)-C(sp3)
bond
formations
have
been
made
with
nickel-catalyzed
cross-coupling
of
racemic
alkyl
electrophiles
organometallic
reagents
or
nickel-hydride-catalyzed
hydrocarbonation
alkenes.
Herein,
we
report
an
unprecedented
enantioselective
reductive
by
the
direct
utilization
two
different
halides
dual
nickel/photoredox
catalysis
system.
This
highly
selective
coupling
α-chloroboronates
and
unactivated
iodides
furnishes
chiral
secondary
boronic
esters,
which
serve
as
useful
important
intermediates
realm
organic
synthesis
enable
a
desirable
protocol
to
fast
construction
enantioenriched
complex
molecules.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
63(3)
Опубликована: Дек. 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
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(34)
Опубликована: Июнь 16, 2023
Abstract
Operationally
simple
strategies
to
assemble
boron
containing
organic
frameworks
are
highly
enabling
in
synthesis.
While
conventional
retrosynthetic
logic
has
engendered
many
platforms
focusing
on
the
direct
formation
of
C−B
bonds,
α‐boryl
radicals
have
recently
reemerged
as
versatile
open‐shell
alternatives
access
organoborons
via
adjacent
C−C
bond
formation.
Direct
light‐enabled
α‐activation
is
currently
contingent
photo‐
or
transition
metal‐catalysis
activation
efficiently
generate
radical
species.
Here,
we
disclose
a
facile
α‐halo
boronic
esters
using
only
visible
light
and
Lewis
base
enable
homolytic
scission.
Intermolecular
addition
styrenes
facilitates
rapid
construction
E
‐allylic
esters.
The
simplicity
permits
strategic
merger
this
construct
with
selective
energy
transfer
catalysis
complimentary
stereodivergent
synthesis
Z
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(16), С. 8781 - 8787
Опубликована: Март 17, 2023
The
substituted
benzene
derivatives
are
essential
to
organic
synthesis,
medicinal
chemistry,
and
material
science.
However,
the
1,3-di-
1,3,5-trisubstituted
benzenes
far
less
prevalent
in
small-molecule
drugs
than
other
substitution
patterns,
likely
due
lack
of
robust,
efficient,
convenient
synthetic
methods.
Here,
we
report
a
Mo-catalyzed
intermolecular
deoxygenative
benzene-forming
reaction
readily
available
ynones
allylic
amines.
A
wide
range
unsymmetric
unfunctionalized
were
obtained
up
88%
yield
by
using
commercially
molybdenum
catalyst.
potential
method
was
further
illustrated
transformations,
scale-up
derivatization
bioactive
molecules.
Preliminary
mechanistic
studies
suggested
that
this
process
might
proceed
through
aza-Michael
addition/[1,5]-hydride
shift/cyclization/aromatization
cascade.
This
strategy
not
only
provided
facile,
modular
approach
various
meta-substituted
but
also
demonstrated
catalysis
challenging
cross-coupling
reactions.
α-halo
alkylboronic
esters,
acting
as
ambiphilic
synthons,
play
a
pivotal
role
versatile
intermediates
in
fields
like
pharmaceutical
science
and
organic
chemistry.
The
sequential
transformation
of
carbon-boron
carbon-halogen
bonds
into
broad
range
carbon-X
allows
for
programmable
bond
formation,
facilitating
the
incorporation
multiple
substituents
at
single
position
streamlining
synthesis
complex
molecules.
Nevertheless,
synthetic
potential
these
compounds
is
constrained
by
limited
reaction
patterns.
Additionally,
conventional
methods
often
necessitate
use
bulk
toxic
solvents,
exhibit
sensitivity
to
air/moisture,
rely
on
expensive
metal
catalysts,
involve
extended
times.
In
this
report,
ball
milling
technique
introduced
that
overcomes
limitations,
enabling
external
catalyst-free
multicomponent
coupling
aryl
diazonium
salts,
alkenes,
simple
halides.
This
approach
offers
general
straightforward
method
obtaining
diverse
array
thereby
paving
way
extensive
utilization
synthons
fine
chemicals.
ACS Catalysis,
Год журнала:
2023,
Номер
14(1), С. 547 - 553
Опубликована: Дек. 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,
Год журнала:
2024,
Номер
146(8), С. 5605 - 5613
Опубликована: Фев. 14, 2024
Carbonyl
is
highly
accessible
and
acts
as
an
essential
functional
group
in
chemical
synthesis.
However,
the
direct
catalytic
deoxygenative
functionalization
of
carbonyl
compounds
via
a
putative
metal
carbene
intermediate
formidable
challenge
due
to
requirement
high
activation
energy
for
cleavage
strong
C═O
double
bonds.
Here,
we
report
class
bench
stable
readily
available
Cp*Mo(II)-complexes
efficient
deoxygenation
catalysts
that
could
catalyze
intermolecular
coupling
with
alkynes.
Enabled
by
this
powerful
Cp*Mo(II)-catalyst,
various
valuable
heteroarenes
(10
different
classes)
were
obtained
generally
good
yields
remarkable
chemo-
regioselectivities.
Mechanistic
studies
suggested
reaction
might
proceed
sequence
bonds
cleavage,
carbene-alkyne
metathesis,
cyclization,
aromatization
processes.
This
strategy
not
only
provided
general
platform
rapid
preparation
but
also
opened
new
window
applications
Cp*Mo(II)-catalysts
organic