Aerobic
nitro-nitrite
isomerization
of
secondary
nitroalkanes
is
postulated
to
proceed
via
the
intermediacy
α-nitro
alkyl
radical,
where
corresponding
Nef-type
products,
ketones,
and
nitrogen
monoxide
can
be
obtained
as
byproducts.
To
explore
catalytic
aerobic
carbooximation
alkenes
using
nitroalkanes,
phase-transfer
catalysis
KSeCN
TBAI
has
been
developed.
The
current
utilizes
both
radical
sources
in
water
without
external
oxidants
prefunctionalized
nitroalkanes.
Acta Pharmaceutica Sinica B,
Год журнала:
2023,
Номер
14(3), С. 1030 - 1076
Опубликована: Ноя. 18, 2023
Synthetic
chemistry
plays
an
indispensable
role
in
drug
discovery,
contributing
to
hit
compounds
identification,
lead
optimization,
candidate
drugs
preparation,
and
so
on.
As
Nobel
Prize
laureate
James
Black
emphasized,
"the
most
fruitful
basis
for
the
discovery
of
a
new
is
start
with
old
drug"
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(12)
Опубликована: Янв. 26, 2024
Abstract
In
this
report,
we
describe
the
use
of
amino‐λ
3
‐iodanes
in
electrophilic
amination
arylboronic
acids
and
boronates.
Iodine(III)
reagents
with
transferable
amino
groups,
including
one
an
NH
2
group,
were
synthesized
used
amination,
allowing
synthesis
a
wide
range
primary
secondary
(hetero)arylamines.
Mechanistic
studies
by
DFT
calculations
indicate
that
reaction
proceeds
through
process
from
tetravalent
borate
complex
B−N
dative
bond.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(20), С. 14136 - 14148
Опубликована: Апрель 20, 2024
An
unprecedented
chiral
bisphosphine-catalyzed
asymmetric
Staudinger/aza-Wittig
reaction
of
2,2-disubstituted
cyclohexane-1,3-diones
is
reported,
enabling
the
facile
access
a
broad
range
cis-3a-arylhydroindoles
in
high
yields
with
excellent
enantioselectivities.
The
key
to
success
this
work
relies
on
first
application
bisphosphine
DuanPhos
reaction.
effective
reductive
system
has
been
established
address
challenging
PV═O/PIII
redox
cycle
associated
catalyst.
In
addition,
comprehensive
experimental
and
computational
investigations
were
carried
out
elucidate
mechanism
Leveraging
newly
developed
chemistry,
enantioselective
total
syntheses
several
crinine-type
Amaryllidaceae
alkaloids,
including
(+)-powelline,
(+)-buphanamine,
(+)-vittatine,
(+)-crinane,
have
accomplished
remarkable
conciseness
efficiency.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(28), С. 19160 - 19167
Опубликована: Июль 3, 2024
Boronic
acids
and
esters
are
highly
regarded
for
their
safety,
unique
reactivity,
versatility
in
synthesizing
a
wide
range
of
small
molecules,
bioconjugates,
materials.
They
not
exploited
biocatalytic
synthesis,
however,
because
enzymes
that
can
make,
break,
or
modify
carbon–boron
bonds
rare.
We
wish
to
combine
the
advantages
boronic
molecular
assembly
with
biocatalysis,
which
offers
potential
unsurpassed
selectivity
efficiency.
Here,
we
introduce
an
engineered
protoglobin
nitrene
transferase
catalyzes
new-to-nature
amination
using
hydroxylamine.
Initially
targeting
aryl
acids,
show
enzyme
produce
array
anilines
high
yields
total
turnover
numbers
(up
99%
yield
>4000
TTN),
water
boric
acid
as
only
byproducts.
also
demonstrate
is
effective
bench-stable
esters,
hydrolyze
situ
corresponding
acids.
Exploring
enzyme's
capacity
enantioselective
catalysis,
found
racemic
alkyl
ester
affords
enantioenriched
amine,
transformation
achieved
chemocatalysts.
The
formation
exclusively
unrearranged
product
during
radical
clock
reaction's
stereospecificity
support
two-electron
process
akin
1,2-metallate
shift
mechanism.
developed
enables
new
routes
chiral
amines.
Chinese Journal of Chemistry,
Год журнала:
2023,
Номер
42(4), С. 351 - 355
Опубликована: Сен. 28, 2023
Comprehensive
Summary
In
this
paper,
we
have
developed
a
decarboxylative
amination
of
carboxylic
acids
with
nitroarenes
for
the
synthesis
secondary
amines.
The
protocol
is
performed
at
mild
conditions
without
use
noble
metals
as
catalysts.
A
wide
range
structurally
diverse
amines
could
be
obtained
in
good
yields
(up
to
94%)
functional
group
tolerance.
This
transformation
shows
excellent
selectivity,
avoiding
generation
over
alkylated
byproducts.
Green Synthesis and Catalysis,
Год журнала:
2022,
Номер
4(2), С. 135 - 149
Опубликована: Окт. 27, 2022
The
special
electronic
configuration
of
phosphorus
atoms
endows
organophosphorus
reagents
with
unique
chemical
properties,
which
enable
them
to
be
used
catalyze
various
organic
reactions,
such
as
the
Wittig
reaction,
Staudinger
Appel
reaction
and
Mitsunobu
reaction.
However,
catalytic
process
will
accompanied
by
generation
large
amounts
phosphine
oxide
waste,
resulting
in
reduction
atom
utilization
it
is
difficult
separate
product.
Therefore,
essential
explore
a
greener
more
sustainable
synthesis
route
based
on
cycle
model.
This
paper
summarizes
recycling
or
without
reducing
agents
reviews
related
developments
recent
decades:
from
addition
stoichiometric
strong
agents,
design
ring
phosphines
specific
structures,
development
new
energy
inputs
(electrochemistry),
series
compounds
activate
P(V)O
double
bond,
driving
through
transformation.
review
also
points
out
potential
this
field
future,
promote
its
progress
direction.
Organic Letters,
Год журнала:
2023,
Номер
25(49), С. 8872 - 8876
Опубликована: Дек. 4, 2023
An
efficient
photocatalytic
C–N
cross-coupling
of
nitroarenes
with
haloarenes
has
been
developed
using
simple
and
cheap
Ni(acac)2
as
a
cocatalyst.
The
reaction
is
confirmed
stepwise
process:
(1)
metal
free
photoinduced
reduction
into
aniline
derivatives
(2)
photo-
Ni-catalyzed
anilines
haloarenes.
conditions
are
mild,
giving
high-value
diarylamines
good
to
excellent
yields
functional
group
tolerance.
Organic & Biomolecular Chemistry,
Год журнала:
2023,
Номер
21(35), С. 7036 - 7051
Опубликована: Янв. 1, 2023
This
review
provides
a
comprehensive
summary
of
the
utilization
ammonia
replacements
in
synthesizing
protected
and
free
primary
amines,
encompassing
both
traditional
reagents
latest
developments.
Chemical Communications,
Год журнала:
2024,
Номер
60(67), С. 8806 - 8823
Опубликована: Янв. 1, 2024
Distinct
reactivity
and
chemoselectives
of
photoexcited
nitroarenes
under
visible
light
irradiation
such
as
reductive
C–N
coupling,
anaerobic
oxidation,
annulation,
scaffold
diversification
via
nitrene
insertion,
etc.
,
are
highlighted.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 21, 2024
Abstract
Electrochemical
reduction
of
2‐allyl‐substituted
nitroarenes
using
a
simple,
undivided
electrochemical
cell
with
non‐precious
electrodes
to
generate
nitroarene
radical
anions
was
developed.
The
anion
intermediates
participate
in
1,5‐hydrogen
atom
transfer
reactions
construct
quinoline
N
‐oxides
bearing
aryl‐,
heteroaryl‐,
alkenyl‐,
benzyl‐,
sulfonyl‐,
or
carboxyl
groups.
