Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(22), С. 12214 - 12223
Опубликована: Май 24, 2023
Simple
aromatic
compounds
like
benzene
are
abundant
feedstocks,
for
which
the
preparation
of
derivatives
chiefly
begins
with
electrophilic
substitution
reactions
or,
less
frequently,
reductions.
Their
high
stability
makes
them
particularly
reluctant
to
participate
in
cycloadditions
under
ordinary
reaction
conditions.
Here,
we
demonstrate
exceptional
ability
1,3-diaza-2-azoniaallene
cations
undergo
formal
(3
+
2)
unactivated
below
room
temperature,
providing
thermally
stable
dearomatized
adducts
on
a
multi-gram
scale.
The
cycloaddition,
tolerates
polar
functional
groups,
activates
ring
toward
further
elaboration.
On
treatment
dienophiles,
cycloadducts
(4
cycloaddition–cycloreversion
cascade
yield
substituted
or
fused
arenes,
including
naphthalene
derivatives.
overall
sequence
results
transmutation
arenes
through
an
exchange
carbons:
two-carbon
fragment
from
original
is
replaced
another
incoming
dienophile,
introducing
unconventional
disconnection
synthesis
ubiquitous
building
blocks.
Applications
this
two-step
acenes,
isotopically
labeled
molecules,
and
medicinally
relevant
demonstrated.
Chemical Reviews,
Год журнала:
2023,
Номер
123(19), С. 11269 - 11335
Опубликована: Сен. 26, 2023
Late-stage
functionalization
(LSF)
constitutes
a
powerful
strategy
for
the
assembly
or
diversification
of
novel
molecular
entities
with
improved
physicochemical
biological
activities.
LSF
can
thus
greatly
accelerate
development
medicinally
relevant
compounds,
crop
protecting
agents,
and
functional
materials.
Electrochemical
synthesis
has
emerged
as
an
environmentally
friendly
platform
transformation
organic
compounds.
Over
past
decade,
electrochemical
late-stage
(eLSF)
gained
major
momentum,
which
is
summarized
herein
up
to
February
2023.
Chemical Society Reviews,
Год журнала:
2022,
Номер
51(15), С. 6291 - 6306
Опубликована: Янв. 1, 2022
This
review
is
a
systematic
summary
of
radical
deuteration
with
four
reaction
types:
reductive
deuteration,
defunctionalization–deuteration,
hydrogen–deuterium
(H/D)
exchange
and
deuteroalkylation.
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Фев. 21, 2025
Deuterated
amines
are
key
building
blocks
for
drug
synthesis
and
the
identification
of
metabolites
new
pharmaceuticals,
which
drives
search
general,
efficient,
widely
applicable
methods
selective
such
compounds.
Here,
we
describe
a
multifunctional
phosphorus-doped
carbon-supported
Fe
catalyst
with
highly
dispersed
isolated
metal
sites
that
allow
tandem
reductive
amination-deuteration
sequences.
The
optimal
phosphorus-modified
Fe-based
shows
excellent
performance
in
terms
both
reactivity
regioselectivity
wide
range
deuterated
anilines,
amines,
bioactive
complexes,
drugs
(>50
examples).
Experiments
on
gram
scale
recycling
show
application
potential
this
method.
Beyond
direct
applicability
developed
method,
described
approach
opens
perspective
development
single-atom
catalysts
other
value-adding
organic
syntheses.
play
crucial
role
as
identifying
novel
pharmaceuticals.
This
study
introduces
dual-functional
iron
efficiently
enables
amination
deuteration
one-pot
process,
utilizing
H2
reducing
agent
cost-effective
D2O
deuterium
source.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(22), С. 9570 - 9575
Опубликована: Май 25, 2022
Deuterated
organic
compounds
have
become
increasingly
important
in
many
areas;
however,
it
remains
challenging
to
install
deuterium
site-selectively
unactivated
aliphatic
positions
with
control
of
the
degree
deuteration.
Here,
we
report
a
Cu-catalyzed
degree-controlled
deacylative
deuteration
diverse
alkyl
groups
methylketone
(acetyl)
moiety
as
traceless
activating
group.
The
use
N-methylpicolino-hydrazonamide
(MPHA)
promotes
efficient
aromatization-driven
C–C
cleavage.
Mono-,
di-,
and
trideuteration
at
specific
sites
can
be
selectively
achieved.
reaction
is
redox-neutral
broad
functional
group
tolerance.
utility
this
method
has
been
demonstrated
forming
complete
set
deuterated
ethyl
groups,
merging
Diels–Alder
reaction,
net
devinylative
deuteration,
synthesis
d2-analogue
Austedo.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
62(3)
Опубликована: Ноя. 9, 2022
Decarboxylative
protonation
is
a
general
deletion
tactic
to
replace
polar
carboxylic
acid
groups
with
hydrogen
or
its
isotope.
Current
methods
rely
on
the
pre-activation
of
acids,
non-sustainable
sources,
and/or
expensive/highly
oxidizing
photocatalysts,
presenting
challenges
their
wide
adoption.
Here
we
show
that
cooperative
iron/thiol
catalyst
system
can
readily
achieve
this
transformation,
hydrodecarboxylating
range
activated
and
unactivated
acids
overcoming
scope
limitations
in
previous
direct
methods.
The
reaction
scaled
batch
configuration
be
directly
performed
deuterated
solvent
afford
high
yields
d-incorporated
products
excellent
isotope
incorporation
efficiency;
characteristics
not
attainable
photocatalyzed
approaches.
Preliminary
mechanistic
studies
indicate
radical
mechanism
kinetic
results
(KIE=1)
are
consistent
light-limited
reaction.
Chinese Journal of Chemistry,
Год журнала:
2023,
Номер
42(10), С. 1145 - 1156
Опубликована: Дек. 26, 2023
Comprehensive
Summary
The
deuteration
of
organic
compounds
has
attracted
more
attentions
in
recent
years
for
the
potential
applications
new
drug
discovery
and
synthetic
chemistry.
For
this
purpose,
many
efficient
deuterium
labeling
methodologies
have
been
developed,
including
hydrogen
isotope
exchange
(HIE),
reductive
deuteration,
dehalogenative
that
allow
synthesis
selectively
deuterated
compounds.
In
last
few
years,
great
breakthroughs
selective
achieved
interest
molecules
is
rising.
review,
we
summarized
developments
since
2021.
Several
types
key
processes
incorporation
reactions,
H/D
exchange,
are
introduced
discussed.
Key
Scientists
2000s,
Derdau
Atzrodt's
group
made
contributions
to
directing
assisted
noble‐metal
catalyzed
arenes
labeled
During
same
period,
Sajiki
co‐workers
completed
a
series
reactions
by
heterogeneous
platinum‐group
metal
catalysts.
Since
2015,
Gregory
Pieters
developed
ruthenium
catalysts
exchange.
2016,
Chirik's
presence
homogeneous
iron
complex.
David
MacMillan
coworkers
photocatalyzed
HIE
α‐amino
C(sp
3
)–H
bonds.
From
2020,
nanoelectrodes
were
designed
deuterations
unactivated
unsaturated
bonds
Zhang's
group.
Recently,
Beller's
several
strategies
isotopic
using
earth‐abundant
Our
review
latest
important
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(17)
Опубликована: Март 5, 2023
Amide
is
one
of
the
most
widespread
functional
groups
in
organic
and
bioorganic
chemistry,
it
would
be
valuable
to
achieve
stereoselective
C(sp3
)-H
functionalization
amide
molecules.
Palladium(II)
catalysis
has
been
prevalently
used
C-H
activation
chemistry
past
decades,
however,
due
weakly-coordinating
feature
simple
amides,
challenging
their
direct
with
enantiocontrol
by
PdII
catalysis.
Our
group
developed
sulfoxide-2-hydroxypridine
(SOHP)
ligands,
which
exhibited
remarkable
activity
Pd-catalyzed
C(sp2
activation.
In
this
work,
we
demonstrate
that
chiral
SOHP
ligands
served
as
an
ideal
solution
enantioselective
amides.
Herein,
report
efficient
asymmetric
/SOHP-catalyzed
β-C(sp3
arylation
aliphatic
tertiary
ligand
plays
a
key
role
deprotonation-metalation
step.
