Angewandte Chemie,
Journal Year:
2022,
Volume and Issue:
134(46)
Published: Oct. 17, 2022
Abstract
Two
catalytic
systems
have
been
developed
for
the
arylboration
of
endocyclic
enecarbamates
to
deliver
synthetically
versatile
borylated
saturated
N‐heterocycles
in
good
regio‐
and
diastereoselectivities.
A
Cu/Pd
dual
reaction
enables
synthesis
borylated,
α‐arylated
azetidines,
while
a
Ni‐catalysed
efficiently
functionalizes
5‐,
6‐,
7‐membered
enecarbamates.
In
case
Cu/Pd‐system,
remarkable
additive
effect
was
identified
that
allowed
broader
scope.
The
products
are
useful,
as
demonstrated
by
manipulations
boronic
ester
access
biologically
active
compounds.
Asian Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
12(10)
Published: Aug. 21, 2023
Abstract
An
additive‐free
three‐component
reaction
of
allenamides
with
in
situ
generated
trifluoromethylnitrones
has
been
uncovered.
The
afforded
an
interesting
class
trifluoromethylated
methyleneisoxazolidines
under
mild
conditions.
Additionally,
a
gram‐scale
and
the
reductive
transformation
isoxazolidines
to
aminomethylated
allyl
alcohol
illustrate
high
synthetic
utility
present
strategy.
Chemical Communications,
Journal Year:
2023,
Volume and Issue:
59(97), P. 14423 - 14426
Published: Jan. 1, 2023
A
visible-light-induced
cycloaddition
between
2-alkenylarylisocyanides
and
cyclopropylanilines
is
reported.
This
cascade
radical
reaction
constructs
two
new
C-C
bonds
rings
to
afford
3-aminotetrahydro-1H-carbazols
with
high
atom
step
economy.
The
mechanism
rationalized
as
involving
sequential
distonic
cation
formation/isocyanide
insertion/5-exo-trig
cyclization/intramolecular
iminium
ion
addition/tautomerization.
Angewandte Chemie,
Journal Year:
2022,
Volume and Issue:
135(4)
Published: Oct. 14, 2022
Abstract
The
field
of
strain‐driven,
radical
formal
cycloadditions
is
experiencing
a
surge
in
activity
motivated
by
renaissance
free
chemistry
and
growing
demand
for
sp
3
‐rich
ring
systems.
former
has
been
driven
large
part
the
rise
photoredox
catalysis,
latter
adoption
“Escape
from
Flatland”
concept
medicinal
chemistry.
In
years
since
these
broader
trends
emerged,
dozens
cycloadditions,
including
catalytic,
asymmetric
variants,
have
developed
that
operate
via
mechanisms.
While
cyclopropanes
studied
most
extensively,
variety
strained
systems
are
amenable
to
design
analogous
reactions.
Many
processes
generate
lucrative,
functionally
decorated
difficult
access
other
means.
Herein,
we
summarize
recent
efforts
this
area
analyze
state
field.
Abstract
The
study
of
cycloaddition
mechanisms
is
central
to
the
fabrication
extended
sp2
carbon
nanostructures
such
as
spin-chains.
Reaction
modeling
in
this
context
has
focused
mostly
on
putative,
energetically
preferred,
exothermic
products
with
limited
consideration
for
symmetry
allowed
or
forbidden
mechanistic
effects.
To
classify
and
optimize
reaction
modern
topological
tools
can
be
explored.
Here,
we
introduce
a
scheme
classifying
symmetry-forbidden
coordinates
Woodward-Hoffmann
correlation
diagrams.
Topological
classifiers
grant
access
pathways
diagrams
same
footing,
purpose
elucidating
polycyclic
aromatic
azomethine
ylide
(PAMY)
cycloadditions
pentacene–yielding
hydrocarbons
an
isoindole
core
solid-state
surfaces,
characterized
by
mass
spectrometry
scanning
tunneling
microscopy,
respectively.
By
means
tight-binding
model
density
functional
theory
(DFT)
find
topologically-allowed
endothermic
mechanism.
Our
work
unveils
classification
crucial
element
nanographene
engineering,
highlights
its
fundamental
role
design
on-surface
chemical
reactions,
while
underscoring
that
topologically-forbidden.
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
137(1)
Published: Aug. 14, 2024
Abstract
Asymmetric
diboration
of
terminal
alkenes
is
well
established,
and
subsequent
selective
functionalization
the
less
hindered
primary
boronic
ester
commonly
achieved.
Conversely,
sterically
accessible
secondary
remains
challenging.
An
alternative
way
to
control
chemoselective
bis(boron)
compounds
by
engendering
different
Lewis
acidity
two
boryl
moieties,
since
reactivity
would
then
be
dictated
instead
sterics.
We
report
herein
regio‐
enantioselective
Pt‐catalyzed
unactivated
with
(pin)B−B(dan).
A
broad
range
cyclic
undergo
furnish
differentiable
1,2‐bis(boron)
high
levels
enantiocontrol,
giving
access
a
wide
variety
novel
building
blocks
from
common
intermediate.
The
reaction
places
acidic
B(dan)
group
at
position
resulting
1,2‐bisboryl
alkanes
transformations
B(pin)
located
more
position.
regioselectivity
has
been
studied
DFT
calculations
believed
originate
trans
influence,
which
lowers
activation
barrier
for
formation
regioisomer
that
weaker
electron
donor
[B(pin)
vs
B(dan)]
opposite
strong
(alkyl
group)
in
platinum
complex.
Angewandte Chemie,
Journal Year:
2022,
Volume and Issue:
134(46)
Published: Oct. 17, 2022
Abstract
Two
catalytic
systems
have
been
developed
for
the
arylboration
of
endocyclic
enecarbamates
to
deliver
synthetically
versatile
borylated
saturated
N‐heterocycles
in
good
regio‐
and
diastereoselectivities.
A
Cu/Pd
dual
reaction
enables
synthesis
borylated,
α‐arylated
azetidines,
while
a
Ni‐catalysed
efficiently
functionalizes
5‐,
6‐,
7‐membered
enecarbamates.
In
case
Cu/Pd‐system,
remarkable
additive
effect
was
identified
that
allowed
broader
scope.
The
products
are
useful,
as
demonstrated
by
manipulations
boronic
ester
access
biologically
active
compounds.
