Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(11), P. 2266 - 2270
Published: March 7, 2024
A
sustainable,
cyanide-free
synthesis
of
alkyl
nitriles
via
the
aerobic
oxidative
deconstruction
unstrained
cycloalkanones
with
ammonium
salts
has
been
developed.
Using
inexpensive
and
stable
as
nitrogen
source,
a
variety
containing
distal
carbonyl
group
were
obtained
in
good
yields
under
visible-light-promoted
iron
catalysis.
This
protocol
is
characterized
by
mild
conditions,
abundant
environmentally
benign
materials,
high
atom
step
economy
minimal
waste
generation.
The
primary
mechanism
study
revealed
that
Science,
Journal Year:
2023,
Volume and Issue:
381(6653), P. 75 - 81
Published: July 6, 2023
Skeletal
ring
enlargement
is
gaining
renewed
interest
in
synthetic
chemistry
and
has
recently
focused
on
insertion
of
one
or
two
atoms.
Strategies
for
heterocyclic
expansion
through
small-ring
remain
elusive,
although
they
would
lead
to
the
efficient
formation
bicyclic
products.
Here,
we
report
a
photoinduced
dearomative
thiophenes
by
bicyclo[1.1.0]butanes
produce
eight-membered
rings
under
mild
conditions.
The
value,
broad
functional-group
compatibility,
excellent
chemo-
regioselectivity
were
demonstrated
scope
evaluation
product
derivatization.
Experimental
computational
studies
point
toward
photoredox-induced
radical
pathway.
Chemical Science,
Journal Year:
2023,
Volume and Issue:
14(11), P. 2954 - 2959
Published: Jan. 1, 2023
We
report
a
convenient
protocol
for
nitrogen
atom
insertion
into
indenes
to
afford
isoquinolines.
The
strategy
further
enables
the
synthesis
of
pyridines
from
cyclopentadienes
and
facile
access
15
N
labelled
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:
2023,
Volume and Issue:
145(32), P. 17570 - 17576
Published: Aug. 3, 2023
In
this
study,
we
describe
the
direct
insertion
of
an
intramolecular
nitrogen
atom
into
aromatic
C–C
bond.
transformation,
carbamoyl
azides
are
activated
by
a
Rh
catalyst
and
subsequently
directly
inserted
bond
arene
ring
to
access
fused
azepine
products.
This
transformation
is
challenging,
owing
existence
competitive
C–H
amination
pathway.
The
use
paddlewheel
dirhodium
complex
Rh2(esp)2
effectively
inhibited
undesired
insertion.
Density
functional
theory
calculations
were
performed
reveal
reaction
mechanism
origin
chemoselectivity
Rh-catalyzed
reactions.
novel
products
highly
robust
allow
for
downstream
diversification.
Acta Pharmaceutica Sinica B,
Journal Year:
2023,
Volume and Issue:
14(3), P. 1030 - 1076
Published: Nov. 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"
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.
