Angewandte Chemie,
Journal Year:
2022,
Volume and Issue:
135(5)
Published: Nov. 8, 2022
Abstract
The
trapping
of
the
elusive
vinylogous
position
a
vinyl
carbene
with
an
aliphatic
C(sp
3
)−H
bond
has
been
achieved
for
first
time
during
silver‐catalyzed
carbene/alkyne
metathesis
(CAM)
process.
A
Tp
x
‐containing
silver
complex
promotes
generation
donor‐acceptor
which
triggers
CAM,
generating
subsequent
donor‐donor
species,
then
undergoes
selective
insertion,
leading
to
synthesis
new
family
benzoazepines.
Density
functional
theory
(DFT)
calculations
unveil
reaction
mechanism,
allows
proposing
that
C−H
insertion
takes
place
in
stepwise
manner,
hydrogen
shift
being
rate
determining
step.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
62(5)
Published: Nov. 8, 2022
The
trapping
of
the
elusive
vinylogous
position
a
vinyl
carbene
with
an
aliphatic
C(sp3
)-H
bond
has
been
achieved
for
first
time
during
silver-catalyzed
carbene/alkyne
metathesis
(CAM)
process.
A
Tpx
-containing
silver
complex
promotes
generation
donor-acceptor
which
triggers
CAM,
generating
subsequent
donor-donor
species,
then
undergoes
selective
insertion,
leading
to
synthesis
new
family
benzoazepines.
Density
functional
theory
(DFT)
calculations
unveil
reaction
mechanism,
allows
proposing
that
C-H
insertion
takes
place
in
stepwise
manner,
hydrogen
shift
being
rate
determining
step.
The Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
88(12), P. 7844 - 7848
Published: Feb. 1, 2023
A
highly
regiospecific
vinylogous
carbene
insertion
protocol
for
direct
asymmetric
C-H
functionalization
of
indoles
with
arylvinyldiazoacetates
has
been
developed.
Under
the
catalysis
simple
Rh(I)/chiral
diene
complexes,
reaction
occurs
solely
at
position
vinylcarbenoid
exceptional
E
selectivity
and
enantiocontrol.
It
provides
an
efficient
way
to
obtain
interesting
class
chiral
indole
scaffolds
bearing
α,β-unsaturated
ester
unit
a
gem-diaryl
carbon
stereocenter
in
good
yields
(≤99%)
excellent
enantioselectivities
(≤96%)
room
temperature.
The Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
88(14), P. 10040 - 10047
Published: July 3, 2023
We
computationally
study
the
mechanistic
pathway
for
synthetically
valuable
cascading
N-H
functionalization
followed
by
C-C
bond-forming
reaction.
The
impetus
to
such
multicomponent
reactions
catalyzed
Rh(I)
arises
from
highly
fluxional
nature
of
onium
ylide
involved,
which
is
often
not
amenable
experimental
detection.
Our
results
throw
light
on
an
interesting
paradigm
where
binding
metal
plays
a
crucial
role.
provides
some
much-needed
insights
expand
scope
these
methodologies
broader
range
asymmetric
reactions.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(29), P. 5509 - 5514
Published: July 13, 2023
A
novel
and
highly
stereoselective
acyclic
1,3-difunctionalization
of
vinyl
metal
carbene
species
has
been
developed
via
Rh(II)/chiral
phosphoric
acid
co-catalyzed
three-component
reactions
vinyldiazoacetates
with
alcohols
imines.
This
innovative
approach
features
excellent
regio-,
diastereo-,
enantioselectivities,
demonstrating
a
broad
scope
functional
group
compatibility.
Notably,
this
is
the
first
example
asymmetric
in
situ-formed
carbenes.
Advanced Synthesis & Catalysis,
Journal Year:
2023,
Volume and Issue:
366(1), P. 121 - 133
Published: Nov. 21, 2023
Abstract
Metal‐catalyzed
asymmetric
alkylation
of
indoles
with
α‐diazoesters
is
well‐known,
however,
the
underlying
mechanisms
this
reaction,
particularly
origin
stereoselectivity,
remain
uncertain.
For
Pd
catalysis,
we
address
cutting‐edge
challenge
from
two
complementary
viewpoints
–
i)
molecular
level
regarding
a
single
catalytically
active
center;
and
ii)
nano‐level
species
investigating
factors
favoring
appearance
preferred
catalytic
centers.
The
formation
was
monitored
by
structural
methods
(NMR
ESI‐MS),
metal
particles
were
characterized
electron
microscopy
(SEM,
EDX).
On
level,
chiral
bipyridine‐
N,N’
‐dioxides
proved
to
be
competent
controllers.
kinetic
DFT
computational
data
revealed
crucial
role
water
in
rate
selectivity
determining
steps
showed
that
enantioselectivity
process
controlled
protodepalladation
step.
nano‐scale,
important
effect
catalyst
precursor
on
overall
reaction
performance
shown.
Synlett,
Journal Year:
2023,
Volume and Issue:
35(03), P. 319 - 324
Published: Aug. 14, 2023
Abstract
Most
of
the
reactivities
donor–acceptor
(D–A)
singlet
carbenes
are
similar
to
metal
carbenoids.
However,
lone
pair
at
carbenoid
carbon,
coordinated
with
metal,
is
free
in
D–A
carbene
thereby
making
it
nucleophilic
as
well.
Herein,
DFT-optimized
structural
features
has
been
investigated
and
compared
rhodium
carbenoid.
It
was
observed
that,
when
a
reacts
cyclic-1,3-diones
different
ethereal
solvents,
sp2
orbital
that
abstracts
proton
from
enol
form
(of
cyclic-1,3-diones)
benzylic
carbocation
an
enolate.
Subsequently,
undergoes
attack
by
O
ether
solvents
then
enolate
afford
desired
ether-linked
products.
Accordingly,
herein
reaction
THF,
which
otherwise
had
failed
work
substrate
reported
amino
etherification
reactions,
worked
DFT-calculated
energy
levels
profile
support
this
reverse
reactivity
carbenes.
Furthermore,
HOMO–LUMO
calculations
indicated
electron-rich
arenes
stabilizes
LUMO
destabilizes
HOMO
increases
yield.
Additionally,
library
37
39
compounds
potential
medicinal
relevance
have
synthesized
good
excellent
yields
using
numerous
cyclic-1,3-diones.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(15), P. 4084 - 4093
Published: Jan. 1, 2024
A
chiral
phosphoric
acid-catalyzed
highly
enantioselective
formal
C–H
insertion
reaction
of
N–H
free
indole
and
pyrrole
with
sulfoxonium
ylides
has
been
developed
(up
to
95%
yield
97%
ee).
