α,β-Desaturation and Formal β-C(sp3)–H Fluorination of N-Substituted Amines: A Late-Stage Functionalization Strategy Enabled by Electrochemistry
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(33), С. 22982 - 22992
Опубликована: Авг. 12, 2024
Incorporation
of
C(sp
Язык: Английский
Trendbericht: Organische Chemie 2025
Nachrichten aus der Chemie,
Год журнала:
2025,
Номер
73(3), С. 40 - 70
Опубликована: Фев. 28, 2025
Abstract
Highlights
von
November
2023
bis
2024:
die
erste
Einelektron‐C–C‐σ‐Bindung
und
Anti‐Bredt‐Verbindung;
gesättigte
Heterocyclen
elektrochemisch
funktionalisieren;
Ausrichten
diskotischer
Flüssigkristalle;
enantioselektive
Wagner‐Meerwein‐Umlagerung
reiner
Aliphaten;
photokatalytisch
Furanen
zu
Pyrrolen;
mit
Ammoniak
primären
Arylaminen;
Metallschrott
recyceln
ionischen
Flüssigkeiten;
terminale
Alkene
Ni‐Katalysatoren
zum
(Z)‐
oder
(E)‐Alken
isomerisieren;neue
Fungizide,
Medikamente
Alkaloide.
A Voltage-Controlled Strategy for Modular Shono-Type Amination
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(42), С. 28663 - 28668
Опубликована: Окт. 14, 2024
Shono-type
oxidation
to
generate
functionalized
heterocycles
is
a
powerful
method
for
late-stage
diversification
of
relevant
pharmacophores;
however,
development
beyond
oxygen-based
nucleophiles
remains
underdeveloped.
The
limited
scope
can
often
be
ascribed
constant
current
electrolysis
resulting
in
potential
drifts
that
oxidize
desired
nucleophilic
partner.
Herein,
we
report
voltage-controlled
strategy
selectively
broad
substrates,
enabling
modular
C-N
bond
formation
from
protected
amine
nucleophiles.
We
implement
an
electroanalytically
guided
workflow
using
cyclic
voltammetry
(CV)
and
differential
pulse
(DPV)
identify
potentials
across
range
heterocyclic
substrates.
Controlled
(CPE)
generates
α-functionalized
products
moderate
good
yields
carbamate-,
sulfonamide-,
benzamide-derived
importance
voltage
control
further
exemplified
through
systematic
study
comparing
our
developed
CPE
(CCE)
protocols.
Voltage-guided
CCE
traditionally
optimized
reveal
the
maintaining
high
selectivity
over
scope;
case
with
morpholine-derived
substrate
illustrates
negative
impact
drifting
under
CCE.
Sulfonamide
drugs,
which
have
significant
overlap
model
are
rendered
competent
CPE.
Lastly,
sequential
C-O
functionalization
difunctionalized
pyrrolidines
broadening
utility
this
reaction.
Язык: Английский
The Electrochemical trans-Chloroformyloxylation of Unactivated Alkenes
Synlett,
Год журнала:
2024,
Номер
35(16), С. 1906 - 1908
Опубликована: Март 20, 2024
Abstract
An
attempted
aryl
selenium-catalyzed
formation
of
cis-chlorohydrins
from
alkenes
was
unsuccessful
but
led
to
an
electrochemical
investigation
for
the
trans-selective
chloroformyloxylation
cyclic
and
acyclic
in
moderate
good
yields.
Interestingly,
when
1,1-disubstituted
were
used,
corresponding
vinyl
chloride
derivatives
obtained,
application
1-phenylcyclohex-1-ene
allyl
derivative.
Язык: Английский
A Voltage-Controlled Strategy for Modular Shono-Type Amination
Опубликована: Июнь 7, 2024
Shono-type
oxidation
to
generate
functionalized
heterocycles
is
a
powerful
method
for
late-stage
diversification
of
relevant
pharmacophores;
how-ever,
development
beyond
oxygen-based
nucleophiles
remains
underdeveloped.
The
limited
scope
can
often
be
ascribed
constant
current
electrolysis
resulting
in
potential
drifts
that
oxidize
desired
nucleophilic
partner.
Herein,
we
report
voltage-controlled
strategy
selectively
broad
substrates,
enabling
modular
C–N
bond
formation
from
protected
amine
nucleophiles.
We
implement
an
electroanalytically-guided
workflow
using
cyclic
voltammetry
(CV)
and
differential
pulse
(DPV)
identify
potentials
across
range
heterocyclic
substrates.
Controlled
(CPE)
generates
-functionalized
products
moderate
good
yields
carbamate-,
sulfonamide-,
benzamide-derived
importance
voltage
control
further
exemplified
two
cases:
(1)
change
selectivity
at
different
with
morpholine
substrate
(2)
analysis
reaction
outcomes
between
Celecoxib
N-Boc
or
N-Ns-pyrrolidine
substrate;
the
latter
requires
more
anodic
than
does
not
yield
product.
Lastly,
sequential
C–O
functionalization
model
difunctionalized
pyrrolidines
broadening
utility
this
reaction.
Язык: Английский
Chemical Tagging of N-Alkylamine-Containing Natural Products and Pharmaceuticals through C(sp3)–H Functionalization
Опубликована: Авг. 23, 2024
Development
of
efficient
protocols
for
introducing
handles
into
natural
products
and
pharmaceutical
agents
that
are
suitable
bioconjugation
is
a
compelling
research
objective.
One
attractive
option
would
involve
chemical
tagging
through
late-stage
C–H
functionalization,
but
such
strategies
uncommon.
The
primary
challenge
lies
in
the
lack
catalyst
systems
can
chemo-
site-selectively
cleave
relatively
inert
bonds.
In
this
study,
we
demonstrate
bioactive
N-alkylamine-based
other
small-molecule
drugs
be
modified
order
to
facilitate
bioconjugation.
Moreover,
show
under
blue
light
irradiation,
flavin
analogues
promote
oxidation
amines
by
sequential
scission
α-
β-amino
Engagement
resulting
enamines
an
inverse
electron-demand
Diels-Alder
process
with
tetrazines
used
achieve
array
structural
modifications.
Notably,
transformation
occurs
mild,
pH-neutral,
aerobic
conditions.
utility
approach
highlighted
facile
synthesis
antibody–drug
conjugates
involving
anti-cancer
agent
irinotecan.
Язык: Английский
Efficient Chloroacetoxylation of Pyrrolidines and Piperidines
Synfacts,
Год журнала:
2024,
Номер
20(06), С. 0569 - 0569
Опубликована: Май 14, 2024
Key
words
electrochemistry
-
pyrrolidines
piperidines
azepanes
chloroacetoxylation
sulfonamides
Язык: Английский
Recent Advances in The Electrochemical Functionalization of N-heterocycles
Organic & Biomolecular Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Янв. 1, 2024
The
review
aims
to
provide
a
clear
picture
of
the
possible
electron
transfer
pathways,
electrochemical
behavior
different
N-heterocycles,
and
functionalization
reagents
achieve
desired
functionalization/modification
N-heterocycles.
Язык: Английский
Electrochemical Desaturation and β-Thiocyanation of Cyclic Amides
Organic Letters,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 19, 2024
The
site-selective
functionalization
of
cyclic
amides
provides
an
attractive
protocol
for
the
synthesis
valuable
molecules.
We
report
herein
electrochemical
desaturation
and
β-thiocyanation
under
external
oxidant-free
conditions.
This
method
exhibits
broad
functional
group
tolerance,
excellent
selectivity,
mild
reaction
conditions
can
be
applied
late-stage
bioactive
Mechanistic
studies
indicate
that
enamide
intermediate
might
involved.
Язык: Английский