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.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
62(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.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(46)
Published: Oct. 17, 2022
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.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(24), P. 4551 - 4555
Published: June 12, 2023
An
enantioselective
intermolecular
[3
+
2]
cycloaddition
of
N-arylcyclopropylamines
with
2-aryl
acrylates/ketones
and
cyclic
ketone-derived
terminal
olefins
via
asymmetric
photoredox
catalysis
is
reported.
A
dual
catalyst
system
involving
DPZ
a
chiral
phosphoric
acid
effective
for
the
transformations,
leading
to
wide
array
valuable
cyclopentylamines
high
yields,
ee's,
drs.
Among
them,
elaborate
modulation
ester
group
acrylates
was
shown
be
in
improving
reactivity,
thereby
enabling
success
transformations.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(15), P. 3294 - 3298
Published: April 3, 2024
A
(3
+
3)
annulation
of
aminocyclopropanes
and
vinyldiazo
compounds
enabled
by
organo-photocatalysis
is
described.
The
reaction
allows
the
regioselective
synthesis
cyclohexenes
bearing
adjacent
amino
carbonyl
groups
with
broad
functional
group
tolerance.
In
a
departure
from
previous
reports,
our
work
demonstrated
that
distonic
radical
cation
can
be
preferentially
intercepted
weakly
nucleophilic
compounds,
followed
an
exclusive
6-endo
cyclization
for
ring
closure.
Based
on
interaction
between
ester
groups,
products
further
converted
to
cyclohexene-fused
1,3-oxazinane
azetidine.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 10, 2025
(+)-Saxitoxin,
a
potent
neurotoxin
and
NaV
blocker,
poses
significant
synthetic
challenges
due
to
its
compact
tricyclic
framework
guanidinium
moieties.
We
report
concise
asymmetric
total
synthesis
featuring
an
intramolecular
[2
+
2]
photocycloaddition
of
alkenylboronate
ester
equipped
with
new
chiral
auxiliary.
This
auxiliary,
compatible
UV
light
easily
exchangeable
on
B(pin)
derivatives,
enabled
high
stereocontrol
through
hydrogen-bond-mediated
transition-state
stabilization.
Our
approach
not
only
introduces
innovative
surrogate
for
Michael
addition,
particularly
addressing
transformations
contra-thermodynamic
barriers,
but
also
highlights
the
potential
boron-enabled
photochemistry
synthesizing
complex
molecules.
Organic & Biomolecular Chemistry,
Journal Year:
2024,
Volume and Issue:
22(26), P. 5242 - 5256
Published: Jan. 1, 2024
This
review
explores
the
significance
of
trifluoromethylnitrones
in
synthesizing
fluorine-containing
compounds,
with
a
particular
focus
on
trifluoromethylated
heterocycles.
It
versatility
trifluoromethylnitrones,
especially
[3
+
2]
cycloaddition
reactions,
highlighting
their
unique
reactivity
various
dienophile
substrates.
Trifluoromethylnitrones
are
valuable
precursors
for
rapid
synthesis
medicinally
important
heterocycles,
including
isoxazolidines,
dihydroisoxazoles,
oxathiazolidines,
β-lactams,
and
aziridines.
These
turn,
serve
as
synthons
lactams
aminoalcohols.
Additionally,
nitrone
chemistry
extends
to
nucleosides
trifluorinated
organoborane
demonstrating
versatility.
While
sharing
similarities
trifluorodiazoethane
reactivity,
offer
distinct
advantages
by
enabling
heterocycles
typically
inaccessible
trifluorodiazoethane.
The Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
89(1), P. 57 - 67
Published: Dec. 18, 2023
A
general
and
efficient
CuI/N-carbazolyl-1H-pyrrole-2-carbohydrazide
catalyst
system
was
developed
for
the
N-arylation
of
cyclopropylamine
using
aryl
bromides
at
room
temperature.
Herein,
5
mol
%
CuI
ligand
were
used
to
synthesize
N-aryl
cyclopropylamines
in
moderate
excellent
yields.
This
protocol
scaled
up
produce
desired
product
gram
levels
has
been
generalized
C–N
coupling
between
amines
Chemistry - A European Journal,
Journal Year:
2022,
Volume and Issue:
28(54)
Published: Aug. 8, 2022
A
scalable
and
efficient
process
for
the
preparation
of
3-borylated
pyrrolidines
by
1,3-dipolar
cycloaddition
N-benzyl
azomethine
ylide
generated
in
situ
has
been
developed.
The
optimized
method
included
use
LiF
DMSO
at
110
°C
was
suitable
α-mono-,
α,β-di-,
α,β,β-trialkyl-,
β,β-(hetera)cycloalkylidene-,
CO2
Et-,
as
well
most
β-(het)aryl-substituted
alkenyl
boropinacolates.
reaction
proceeded
on
a
multigram
scale
providing
with
diverse
substitution
patterns
(including
fused
spirocyclic
ones)
diastereoselective
manner.
Pd(OH)2
-mediated
N-debenzylation
pyrrolidine
hydrochlorides
successfully
performed
to
give
corresponding
bifunctional
building
blocks
an
up
130
g
scale,
thus
substantial
expansion
synthetic
medicinal
chemist's
toolbox.
Other
reactions
trifluoroborates,
Zweifel-Aggarwal
sp3
-sp2
coupling,
oxidative
deborylation
example
C-heteroatom
bond
formation.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
64(1)
Published: Aug. 14, 2024
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.
