ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(17), P. 13343 - 13351
Published: Aug. 22, 2024
Atomic
carbon
and
its
corresponding
masked
analogues
are
exceedingly
underexplored
intermediates
in
synthesis.
Despite
this,
these
reagents
possess
inimitable
reactivity
such
as
the
ability
to
directly
insert
atoms
into
aromatic
frameworks
while
simultaneously
generating
an
additional
bond
at
center
further
diversify
structure.
Herein,
we
report
design
of
orthogonally
reactive
atomic
equivalent
Cl-DADO
demonstrate
application
molecular
editing
indole
pyrrole,
accessing
linchpin-containing
ring-expanded
heterocycles
that
can
be
subsequently
derivatized.
The
value
this
approach
broad
applicability
reagent
highlighted
by
late-stage
skeletal
numerous
natural
products
drug
molecules.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(5), P. 2950 - 2958
Published: Jan. 29, 2024
The
selective
modification
of
nitrogen
heteroaromatics
enables
the
development
new
chemical
tools
and
accelerates
drug
discovery.
While
methods
that
focus
on
expanding
or
contracting
skeletal
structures
are
emerging,
for
direct
exchange
single
core
atoms
remain
limited.
Here,
we
present
a
method
14N
→
15N
isotopic
several
aromatic
heterocycles.
This
isotope
transmutation
occurs
through
activation
heteroaromatic
substrate
by
triflylation
atom,
followed
ring-opening/ring-closure
sequence
mediated
15N-aspartate
to
effect
atom.
Key
success
this
transformation
is
formation
an
isolable
15N-succinyl
intermediate,
which
undergoes
elimination
give
isotopically
labeled
heterocycle.
These
transformations
occur
under
mild
conditions
in
high
yields.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(4), P. 2845 - 2854
Published: Jan. 18, 2024
In
this
report,
we
developed
a
unified
and
standardized
one-pot
sequence
that
converts
pyridine
derivatives
into
1,2-diazepines
by
inserting
nitrogen
atom.
This
skeletal
transformation
capitalizes
on
the
in
situ
generation
of
1-aminopyridinium
ylides,
which
rearrange
under
UV
light
irradiation.
A
thorough
evaluation
key
parameters
(wavelength,
reaction
conditions,
activating
agent)
allowed
us
to
elaborate
simple,
mild,
user-friendly
protocol.
The
model
was
extrapolated
more
than
40
examples,
including
drug
derivatives,
affording
unique
7-membered
structures.
Mechanistic
evidence
supports
transient
presence
diazanorcaradiene
species.
Finally,
pertinent
transformations
products,
ring
contraction
reactions
form
pyrazoles,
were
conducted
paved
way
broad
application
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 2, 2025
We
recently
reported
a
chiral
phosphoric
acid
(CPA)
catalyzed
enantioselective
photomediated
ring
contraction
of
piperidines
and
other
saturated
heterocycles.
By
extruding
single
heteroatom
from
ring,
this
transformation
builds
desirable
C(sp3)–C(sp3)
bonds
in
the
contracted
products;
however,
origins
enantioselectivity
remain
poorly
understood.
In
work,
has
been
explored
across
an
expanded
structurally
diverse
substrate
scope,
revealing
wide
range
enantioselectivities
(0–99%)
using
two
distinct
CPA
catalysts.
Mechanistic
investigations
support
rate-determining
excitation
that
generates
short-lived
achiral
intermediates
are
intercepted
by
enantiodetermining
closure.
The
effects
competitive
uncatalyzed
reactivity
light-driven
reversibility
closure
on
have
elucidated.
Statistical
models
were
built
regressing
scope
against
key
structural
features
products
for
both
resultant
suggested
factors
influence
response
each
catalyst
enabled
rational
modification
pharmaceutically
relevant
target
molecule
to
improve
enantioselectivity.
Finally,
density
functional
theory
(DFT)-based
transition
state
analysis
identified
noncovalent
interactions
with
correlated
unique
selectivity-relevant
uncovered
through
statistical
modeling.
Our
findings
not
only
offer
comprehensive
insight
into
system
but
should
also
aid
future
development
related
CPA-catalyzed
reactions.
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
Chem,
Journal Year:
2024,
Volume and Issue:
10(6), P. 1940 - 1949
Published: June 1, 2024
The
skeletal
editing
of
heteroarenes
introduces
new
disconnections
to
the
chemistry
lexicon,
enabling
interconversion
ring
systems
via
selective
breaking/re-making
carbon
framework.
We
describe
one-pot
transformation
pyridines
into
benzene
derivatives,
using
a
nucleophilic
addition
ring-opening/ring-closing
(ANRORC)
process
with
soft
nucleophiles
such
as
malonate.
Triflic
anhydride
activates
pyridine
ANRORC
synthesis
an
isolable
amine
intermediate,
which
aromatizes
on
simple
heating.
reaction
has
been
exemplified
room
temperature
protocol,
along
direct
syntheses
drug-like,
tertiary-alkylated,
and
isotopically
labeled
benzoates.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(16), P. 5938 - 5943
Published: Jan. 1, 2024
Cyclopropyl-substituted
sulfonium
salts
are
obtained
by
Rh-catalysed
addition
of
α-diazo
dibenzothiophenium
to
olefins.
When
indenes
used
as
substrates,
initially
formed
cyclopropyl
rings
open
with
concomitant
elimination
dibenzothiophene,
enabling
access
2-substituted
naphthalenes.
Chemical Society Reviews,
Journal Year:
2024,
Volume and Issue:
53(10), P. 4926 - 4975
Published: Jan. 1, 2024
In
search
for
the
perfect
wave(length).
This
review
is
dedicated
to
recent
efforts
in
development
of
visible
light
driven
photochemical
strategies
occurring
coloured
organic
compounds.
