Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
63(5)
Published: Dec. 12, 2023
Abstract
3‐Fluorinated
quinolines
and
pyridines
are
prevalent
pharmacophores,
yet
their
synthesis
is
often
challenging.
Herein,
we
demonstrate
that
dibromofluoromethane
as
bromofluorocarbene
source
enables
the
one‐carbon
ring
expansion
of
readily
available
indoles
pyrroles
to
structurally
diverse
3‐fluorinated
pyridines.
This
straightforward
protocol
requires
only
a
short
reaction
time
ten
minutes
can
be
performed
under
air
atmosphere.
Preliminary
investigations
reveal
this
strategy
also
applied
other
valuable
azines
by
using
different
1,1‐dibromoalkanes
bromocarbene
sources.
Science,
Journal Year:
2022,
Volume and Issue:
377(6610), P. 1104 - 1109
Published: Sept. 1, 2022
Compared
with
peripheral
late-stage
transformations
mainly
focusing
on
carbon-hydrogen
functionalizations,
reliable
strategies
to
directly
edit
the
core
skeleton
of
pharmaceutical
lead
compounds
still
remain
scarce
despite
recent
flurry
activity
in
this
area.
Herein,
we
report
skeletal
editing
indoles
through
nitrogen
atom
insertion,
accessing
corresponding
quinazoline
or
quinoxaline
bioisosteres
by
trapping
an
electrophilic
nitrene
species
generated
from
ammonium
carbamate
and
hypervalent
iodine.
This
reactivity
relies
strategic
use
a
silyl
group
as
labile
protecting
that
can
facilitate
subsequent
product
release.
The
utility
highly
functional
group-compatible
methodology
context
several
commercial
drugs
is
demonstrated.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(20), P. 10960 - 10966
Published: May 5, 2023
Azabicyclo[2.1.1]hexanes
(aza-BCHs)
and
bicyclo[1.1.1]pentanes
(BCPs)
have
emerged
as
attractive
classes
of
sp3-rich
cores
for
replacing
flat,
aromatic
groups
with
metabolically
resistant,
three-dimensional
frameworks
in
drug
scaffolds.
Strategies
to
directly
convert,
or
"scaffold
hop",
between
these
bioisosteric
subclasses
through
single-atom
skeletal
editing
would
enable
efficient
interpolation
within
this
valuable
chemical
space.
Herein,
we
describe
a
strategy
hop"
aza-BCH
BCP
nitrogen-deleting
edit.
Photochemical
[2+2]
cycloadditions,
used
prepare
multifunctionalized
frameworks,
are
coupled
subsequent
deamination
step
afford
bridge-functionalized
BCPs,
which
few
synthetic
solutions
currently
exist.
The
modular
sequence
provides
access
various
privileged
bridged
bicycles
pharmaceutical
relevance.
Chemical Reviews,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Sept. 13, 2024
Hypervalent
iodine(III)
compounds
have
found
wide
application
in
modern
organic
chemistry
as
environmentally
friendly
reagents
and
catalysts.
iodine
are
commonly
used
synthetically
important
halogenations,
oxidations,
aminations,
heterocyclizations,
various
oxidative
functionalizations
of
substrates.
Iodonium
salts
arylating
reagents,
while
iodonium
ylides
imides
excellent
carbene
nitrene
precursors.
Various
derivatives
benziodoxoles,
such
azidobenziodoxoles,
trifluoromethylbenziodoxoles,
alkynylbenziodoxoles,
alkenylbenziodoxoles
group
transfer
the
presence
transition
metal
catalysts,
under
metal-free
conditions,
or
using
photocatalysts
photoirradiation
conditions.
Development
hypervalent
catalytic
systems
discovery
highly
enantioselective
reactions
chiral
represent
a
particularly
recent
achievement
field
chemistry.
Chemical
transformations
promoted
by
many
cases
unique
cannot
be
performed
any
other
common,
non-iodine-based
reagent.
This
review
covers
literature
published
mainly
last
7-8
years,
between
2016
2024.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(32), P. 22829 - 22839
Published: Aug. 1, 2024
The
molecular
editing
of
ketones
represents
an
appealing
strategy
due
to
its
ability
maximize
the
structural
diversity
ketone
compounds
in
a
straightforward
manner.
However,
developing
efficient
methods
for
arbitrary
modification
ketonic
molecules,
particularly
those
integrated
within
complex
skeletons,
remains
significant
challenge.
Herein,
we
present
unique
recasting
that
involves
radical
acylation
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(43), P. 23771 - 23780
Published: Oct. 18, 2023
Given
the
importance
of
cyclic
frameworks
in
molecular
scaffolds
and
drug
discovery,
it
is
intriguing
to
precisely
forge
manipulate
ring
systems
synthetic
chemistry.
In
this
field,
intermolecular
synthesis
densely
substituted
cyclobutanes
with
precise
diastereocontrol
under
simple
reaction
conditions
remains
a
challenge.
Herein,
photoredox
strategy
for
difunctionalization
bicyclo[1.1.0]butanes
(BCBs)
high
regio-
syn-selectivity
disclosed.
C-S
σ-bond
cleavage
partially
unsaturated
sulfur-containing
bifunctional
reagents
an
overall
strain-release-driven
process
enables
thio-alkynylation,
-alkenylation,
-allylation
BCBs
mild
demonstrates
generality
protocol.
Mechanistic
studies
suggest
that
intermediacy
distonic
radical
cations
might
be
key
efficient
scission
σ-bonds
origin
diastereoselectivity.
Chemistry - A European Journal,
Journal Year:
2023,
Volume and Issue:
29(28)
Published: March 7, 2023
Abstract
Asymmetric
[3+2]
cycloaddition
reactions
are
fascinating
and
powerful
methods
for
the
synthesis
of
enantioenriched
pyrrolidines
up
to
four
stereocentres.
Pyrrolidines
important
compounds
both
biology
organocatalytic
applications.
This
review
summarizes
most
recent
advances
in
enantioselective
by
cycloadditions
azomethine
ylides
using
metal
catalysis.
It
has
been
organized
type
catalysis
used
further
arranged
complexity
nature
dipolarophile.
The
presentation
each
reaction
highlights
their
advantages
limitations.
