Research Square (Research Square),
Journal Year:
2023,
Volume and Issue:
unknown
Published: April 18, 2023
Abstract
The
nucleophilic
substitution
reaction
(S
N
2)
is
one
of
the
oldest,
yet
very
useful
organic
transformations
and
has
found
widespread
applications
for
synthesis
drugs
natural
products.
Typically,
cyanide,
oxygen,
nitrogen,
sulfur,
or
phosphorous
nucleophiles
replace
a
halogen
sulfonyl
ester
leaving
group
to
form
new
bond
between
nucleophile
electrophile.
Isocyanides
display
an
unusual
versatile
chemistry
based
on
their
C-centered
lone
pair
s
p
*
frontier
orbitals
leading
radical,
multicomponent
reactions.
Surprisingly,
character
isocyanides
never
been
explored
in
S
2
We
discovered
that
react
as
reactions
with
alkyl
halides
general
manner
afford
highly
substituted
secondary
amides
by
situ
hydrolysis
intermediate
nitrilium
ion.
innovative
3-component
broad
scope
regarding
structures
isocyanide
electrophile
components,
functional
compatibility,
scalability,
use
late-stage
modification
drug
complex
compounds
otherwise
not
easily
accessible
from
simple
precursors.
chemical
space
only
different
but
nearly
doubled
size
compared
classical
amid
coupling.
Significantly,
comprises
Umpolung
amide
carbanion
synthon
R-NHC(-)=O,
alternative
Pharmaceutical Fronts,
Journal Year:
2023,
Volume and Issue:
05(04), P. e227 - e242
Published: Dec. 1, 2023
The
Pictet–Spengler
reaction
is
one
of
the
important
methodological
arsenals
in
synthetic
and
medicinal
chemistry,
acting
as
an
amenable
tool
for
preparing
tetrahydroisoquinoline,
tetrahydro-β-carbolines,
polycyclic
skeletons,
value-added
products.
More
than
100
years
after
its
initial
discovery,
reaction's
response
has
not
withdrawn
from
stage,
but
it
once
again
become
focus
attention
with
new
features.
review
summarizes
recent
advances
Pictet–Spengler-based
multicomponent
reactions
2007
to
2022,
including
three-component
four-component
cyclization
presence
metal
catalysts,
organocatalysts,
biological
enzyme
so
on.
These
protocols
provide
atom-/step
economic
approach
synthesis
a
library
chemical
entities.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(9), P. 1908 - 1913
Published: Feb. 26, 2024
An
intermolecular
controllable
Pd-catalyzed
spirocyclization
of
isocyano
cycloalkenes
has
been
developed,
offering
efficient
and
selective
approaches
toward
spirocyclic
hydropyrrole
scaffolds.
2-Azaspiro-1,7-dienes
could
be
obtained
through
a
"chain-walking"
process
with
aryl/vinyl
iodides
as
electrophiles,
while
the
normal
Heck
product
2-azaspiro-1,6-dienes
were
selectively
generated
when
aryl
triflates
used
coupling
partner
isocyanides.
Mechanistic
studies
suggested
that
counteranion
Pd(II)
intermediate
played
crucial
role
in
regioselectivity
control.
Dihydropyrrole-fused
5,6,7-membered
spirocycles
switchably
accessed
under
mild
conditions
wide
functional
group
tolerance.
ACS Omega,
Journal Year:
2022,
Volume and Issue:
8(1), P. 1577 - 1587
Published: Dec. 16, 2022
Described
herein
is
a
concise
and
practical
direct
amidation
at
the
C-3
position
of
quinoxalin-2(1H)-ones
through
an
acid-promoted
carbamoylation
with
isocyanide
in
water.
In
this
conversion,
environmentally
friendly
water
commercial
inexpensive
were
used
as
solvent
reagent,
respectively.
This
study
not
only
provides
green
efficient
strategy
for
construction
3-carbamoylquinoxalin-2(1H)-one
derivatives
that
can
be
applied
to
synthesis
druglike
structures
but
also
expands
application
organic
chemistry.
Synthesis,
Journal Year:
2024,
Volume and Issue:
56(13), P. 2015 - 2024
Published: June 3, 2024
Abstract
An
efficient
heterogeneous
palladium-catalyzed
carbonylative
coupling
of
aryl
halides
and
organoaluminum
compounds
has
been
developed
using
tert-butyl
isocyanide
as
CO
equivalent.
The
carbonylation
reaction
proceeds
smoothly
in
toluene
with
KOtBu
a
base
at
100
°C
by
10
mol%
an
SBA-15-anchored
bidentate
phosphine
palladium(0)
complex
[2P-SBA-15-Pd(0)]
the
catalyst
provides
general
practical
approach
for
assembly
1,2-diketones
good
to
excellent
yields.
This
heterogenized
palladium
can
be
readily
separated
recovered
via
simple
centrifugation
process
reused
more
than
seven
cycles
almost
consistent
catalytic
efficiency.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 10, 2024
A
novel
strategy
for
the
synthesis
of
various
isochromeno[4,3-c]quinolines
via
palladium-catalyzed
tandem
cyclization
functional
diarylalkynes
with
isocyanides
has
been
developed.
This
approach
features
excellent
chemo-
and
regioselectivities
as
well
good
group
tolerance.
Notably,
6-phenylimino-6H-isochromeno[4,3-c]quinolin-11-amines
11-amino-6H-isochromeno[4,3-c]quinolin-6-ones
can
be
selectively
constructed
by
employing
different
protecting
groups
diarylalkynes.
The
gram-scale
late-stage
modifications
further
demonstrate
synthetic
value
this
method.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 21, 2024
Intramolecular
reactions
between
isocyano
and
iminophosphorane
functions
yield
species
containing
an
embedded
1,3,2-diazaphosphetidine
ring,
as
result
of
the
[2
+
2]
cycloaddition
primary
reactive
product,
cyclic
carbodiimide,
with
a
second
unit
reactant.
DFT
studies
reveal
first
rate-determining
step
entailing
1]
involving
isocyanide
carbon
atom
P═N
double
bond,
further
intervention
dipolar
precursor
intermediate
carbodiimide.
The
ring
final
products
is
shown
to
be
hydrolytically
thermally
labile.
Research Square (Research Square),
Journal Year:
2023,
Volume and Issue:
unknown
Published: April 18, 2023
Abstract
The
nucleophilic
substitution
reaction
(S
N
2)
is
one
of
the
oldest,
yet
very
useful
organic
transformations
and
has
found
widespread
applications
for
synthesis
drugs
natural
products.
Typically,
cyanide,
oxygen,
nitrogen,
sulfur,
or
phosphorous
nucleophiles
replace
a
halogen
sulfonyl
ester
leaving
group
to
form
new
bond
between
nucleophile
electrophile.
Isocyanides
display
an
unusual
versatile
chemistry
based
on
their
C-centered
lone
pair
s
p
*
frontier
orbitals
leading
radical,
multicomponent
reactions.
Surprisingly,
character
isocyanides
never
been
explored
in
S
2
We
discovered
that
react
as
reactions
with
alkyl
halides
general
manner
afford
highly
substituted
secondary
amides
by
situ
hydrolysis
intermediate
nitrilium
ion.
innovative
3-component
broad
scope
regarding
structures
isocyanide
electrophile
components,
functional
compatibility,
scalability,
use
late-stage
modification
drug
complex
compounds
otherwise
not
easily
accessible
from
simple
precursors.
chemical
space
only
different
but
nearly
doubled
size
compared
classical
amid
coupling.
Significantly,
comprises
Umpolung
amide
carbanion
synthon
R-NHC(-)=O,
alternative
