Angewandte Chemie,
Год журнала:
2021,
Номер
133(22), С. 12563 - 12568
Опубликована: Март 22, 2021
Abstract
Asymmetric
aminoazidation
and
diazidation
of
alkenes
are
straightforward
strategies
to
build
value‐added
chiral
nitrogen‐containing
compounds
from
feedstock
chemicals.
They
provide
direct
access
organoazides
complement
enantioselective
diamination.
Despite
the
advances
in
non‐asymmetric
reactions,
asymmetric
or
based
on
acyclic
systems
has
not
been
previously
reported.
Here
we
describe
iron‐catalyzed
intermolecular
styrenes.
The
method
is
practically
useful
requires
relatively
low
loading
catalyst
ligand.
With
mild
reaction
conditions,
can
be
completed
a
20
mmol
scale.
Studies
mechanism
suggest
that
proceeds
via
radical
pathway
involves
stereocontrol
an
free
which
probably
takes
place
through
group
transfer
mechanism.
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
60(22), С. 12455 - 12460
Опубликована: Март 22, 2021
Abstract
Asymmetric
aminoazidation
and
diazidation
of
alkenes
are
straightforward
strategies
to
build
value‐added
chiral
nitrogen‐containing
compounds
from
feedstock
chemicals.
They
provide
direct
access
organoazides
complement
enantioselective
diamination.
Despite
the
advances
in
non‐asymmetric
reactions,
asymmetric
or
based
on
acyclic
systems
has
not
been
previously
reported.
Here
we
describe
iron‐catalyzed
intermolecular
styrenes.
The
method
is
practically
useful
requires
relatively
low
loading
catalyst
ligand.
With
mild
reaction
conditions,
can
be
completed
a
20
mmol
scale.
Studies
mechanism
suggest
that
proceeds
via
radical
pathway
involves
stereocontrol
an
free
which
probably
takes
place
through
group
transfer
mechanism.
Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
365(16), С. 2653 - 2675
Опубликована: Апрель 21, 2023
Abstract
Hypervalent
iodine
compounds
have
found
broad
application
in
modern
organic
chemistry
as
reagents
and
catalysts.
Cyclic
hypervalent
based
on
the
benziodoxole
heterocyclic
system
higher
stability
compared
to
their
acyclic
analogues,
which
makes
possible
preparation
safe
handling
of
with
special
ligands
such
azido,
cyano,
trifluoromethyl
groups.
Numerous
iodine‐substituted
derivatives
been
prepared
utilized
for
transfer
substituent
substrate.
Reactions
these
substrates
can
be
performed
under
metal‐free
conditions,
presence
transition
metal
catalysts,
or
using
photocatalysts
photoirradiation
conditions.
In
this
review,
we
focus
most
recent
synthetic
applications
cyclic
iodine(III)
following
ligands:
N
3
,
NHR,
CN,
CF
SCF
OR,
OAc,
ONO
2
C(=N
)CO
R.
The
review
covers
literature
published
mainly
last
5
years.
Angewandte Chemie International Edition,
Год журнала:
2020,
Номер
60(13), С. 6997 - 7001
Опубликована: Дек. 24, 2020
Abstract
Asymmetric
radical
azidation
for
the
synthesis
of
chiral
alkylazides
remains
a
tremendous
challenge
in
organic
synthesis.
We
report
here
an
unprecedented
highly
enantioselective
acrylamides
catalyzed
by
1
mol
%
copper
catalyst.
The
substrates
were
converted
to
corresponding
high
yield
with
good‐to‐excellent
enantioselectivity.
Notably,
employing
anionic
cyano‐bisoxazoline
(CN‐Box)
ligand
is
crucial
generate
monomeric
Cu
II
azide
species,
rather
than
dimeric
intermediate,
this
azidation.
European Journal of Organic Chemistry,
Год журнала:
2022,
Номер
2022(34)
Опубликована: Июль 28, 2022
Abstract
Organic
azides
have
found
wide
application
in
various
fields
of
science
and
technology.
This
review
summarizes
recently
developed
approaches
to
the
direct,
one‐step
synthesis
diverse
organic
utilizing
hypervalent
iodine
reagents.
The
first
part
deals
with
azidation
using
unstable
azidoiodinanes
generated
situ
from
common
reagents
(such
as
diacetoxyiodobenzene
or
iodosylbenzene)
a
source
azide
anion
(TMSN
3
NaN
).
second
is
dedicated
stable
azidobenziodoxoles
useful
azidating
that
allow
selective
direct
C−H
bonds
double
carbon‐carbon
under
mild
reaction
conditions.
use
eliminates
main
disadvantages
traditional
azides,
such
need
pre‐functionalization
substrates
harsh
Synthetic
made
possible
plethora
including
complex
molecules
at
late
synthetic
stage.
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
60(27), С. 14881 - 14886
Опубликована: Апрель 27, 2021
A
novel
PdII
-catalyzed
enantioselective
oxycarbonylation
of
alkenes
has
been
established.
The
ligand
with
an
ethyl
group
at
the
C-6
position
Pyox
plays
a
significant
role
in
intermolecular
oxypalladation
process,
leading
to
high
reactivity
and
excellent
control.
Compared
conventional
methods,
reaction
itself
features
as
easily
prepared
starting
materials,
mild
operationally
simple
conditions,
insensitivities
air
water.
Moreover,
this
method
allows
for
broad
alkene
substrate
scope,
regio-
enantioselectivities,
scalabilities
wide
array
applications,
provides
useful
route
convenient
straightforward
synthesis
chiral
β-hydroxy
alkylcarboxylic
acids/esters.
Advanced Synthesis & Catalysis,
Год журнала:
2022,
Номер
364(11), С. 1798 - 1848
Опубликована: Апрель 21, 2022
Abstract
This
review
outlines
the
progress
over
recent
years
in
reactions
involving
combined
approach
of
hypervalent
iodine
reagents
and
transition
metals
such
as
palladium,
nickel,
iridium,
gold,
rhodium,
copper,
iron,
ruthenium,
platinum,
silver,
zinc,
rhenium
cobalt.
enables
organic
transformations
complimentary
to
traditional
manifolds.
Hypervalent
play
a
preeminent
role
chemistry
due
their
versatile
reactivity,
heteroatom
ligands
mild
reaction
conditions.
These
combination
metal
compounds
are
used
many
synthetically
useful
oxidation,
rearrangement,
amination,
halogenation,
amidation,
ring‐opening,
cyclization
C−H
C−C
functionalization
reactions,
etc
.
which
discussed
here.
magnified
image
European Journal of Organic Chemistry,
Год журнала:
2022,
Номер
26(2)
Опубликована: Окт. 4, 2022
Abstract
This
Review
summarizes
the
advances
in
catalytic
enantioselective
mono‐
and
difunctionalization
of
alkenes,
highlighting
fundamental
role
ligands.
Several
types
asymmetric
reactions
have
been
developed
involving
different
bonds
formation,
C−O,
C−N
C−C,
urgency
to
go
ahead
search
for
new
ligands
synthetic
methodologies
order
improve
control
over
reaction
selectivity
activity
thus,
increase
applications
synthesis
heterocyclic
scaffolds
biologically
active
compounds.
The
is
organized
into
paragraphs,
which
discuss
type
bond
formed
during
nucleopalladation,
C−N,
C−C
bonds,
involved.
Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
365(3), С. 342 - 354
Опубликована: Янв. 18, 2023
Abstract
MnBr
2
‐catalyzed
oxyazidation
of
fluoroolefins
with
molecular
oxygen
and
TMSN
3
is
reported.
This
method
gives
rise
to
various
useful
fluoroalkylated
β‐hydroxy
aliphatic
azides
in
36%–97%
yields.
Importantly,
this
protocol
features
mild
conditions,
operationally
simple,
gram‐scalable,
it
tolerates
functional
groups
has
been
applied
the
synthesis
diverse
attractive
bioactive
compounds
analogous.
Mechanism
studies
enable
detection
intermediate
indicate
that
a
radical
reaction
process
involved.
The
β‐fluoride
elimination
α‐fluoroalkylated
radicals
via
radical‐polar
crossover
pathway
was
completely
inhibited
reaction.
magnified
image
Chemistry - A European Journal,
Год журнала:
2021,
Номер
27(42), С. 10979 - 10986
Опубликована: Май 12, 2021
Abstract
Ethynylbenziodoxol(on)e
(EBX)
cyclic
hypervalent
iodine
reagents
have
become
popular
for
the
alkynylation
of
radicals
and
nucleophiles,
but
only
offer
limited
possibilities
further
structure
reactivity
fine‐tuning.
Herein,
synthesis
new
N‐heterocyclic
with
increased
structural
flexibility
based
on
amide,
amidine
sulfoximine
scaffolds
is
reported.
Solid‐state
structures
are
reported
analysis
I−C
alkyne
bond
lengths
allowed
assessing
trans
‐effect
different
substituents.
Molecular
electrostatic
potential
(MEP)
maps
reagents,
derived
from
DFT
computations,
revealed
less
pronounced
σ‐hole
regions
sulfonamide‐based
compounds.
Most
reacted
well
in
β‐ketoesters.
The
thiols
afforded
more
variable
yields,
compounds
a
stronger
reacting
better.
In
metal‐mediated
transformations,
gave
inferior
results
when
compared
to
O‐based
EBX
reagents.
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
60(40), С. 21723 - 21727
Опубликована: Авг. 13, 2021
An
oxidative
Pd-catalyzed
intra-intermolecular
dioxygenation
of
(aza-)alkenols
has
been
reported,
with
total
regioselectivity.
To
study
the
stereoselectivity,
different
chiral
ligands
as
well
hypervalent-iodine
compounds
have
compared.
In
particular,
by
using
a
C-6
modified
pyridinyl-oxazoline
(Pyox)
ligand
and
hypervalent
iodine
bearing
an
aromatic
ring,
excellent
enantio-
diastereoselectivity
achieved.
