Intermediate Control: Unlocking Hitherto Unknown Reactivity and Selectivity in N-Conjugated Allenes and Alkynes
Accounts of Chemical Research,
Год журнала:
2025,
Номер
58(2), С. 281 - 298
Опубликована: Янв. 3, 2025
ConspectusControlling
selectivity
through
manipulation
of
reaction
intermediates
remains
one
the
most
enduring
challenges
in
organic
chemistry,
providing
novel
solutions
for
selective
C-C
π-bond
functionalization.
This
approach,
guided
by
activation
principles,
provides
an
effective
method
functional
group
installation,
enabling
direct
synthesis
molecules
that
are
inaccessible
conventional
pathways.
In
particular,
functionalization
N-conjugated
allenes
and
alkynes
has
emerged
as
a
promising
research
focus,
driven
advances
controlling
reactive
strategies.
this
regard,
our
group,
alongside
others,
established
some
new
approaches
have
suitable
platform
functionalized
enamides.
Account
reviews
recent
developments
field,
highlighting
modes
reactivity
selectivity,
atom-economical
functionalizations,
strategies
regio-
stereocontrol,
while
mechanistic
insights
into
related
transformations.Our
study
is
systematically
organized
two
sections
based
on
substrate
type
chronological
progression.
first
section,
we
establish
allenamide-derived
intermediates,
both
allenamide-alkyne
(AA)
cross-coupling
few
electrophile-promoted
hydrofunctionalization
reactions.
The
unprecedented
Pd-catalyzed
achieved
neighboring
chelation,
with
phosphine
ligand
selection
outcome.
parallel,
functionalizations─including
haloalkynylation,
hydrooxycarbonylation,
hydrodifluoroalkylation,
intermolecular
hydroamination─are
strategic
electrophiles
or
their
precursors.Additionally,
findings
demonstrate
how
ynamides'
toward
nucleophiles,
controlled
activator
modulation,
expands
scope
accessible
transformations.
Key
include:
(1)
chemoselective
[2
+
2
2]
annulation
efficient
trapping
N-arylated
nitrilium
ynamides,
(2)
divergent
C-H
indole-derived
vinylogous
ynamides
metal
via
intramolecular
hydroarylation,
(3)
bromoalkynylation-enabled
migration
1,3-alkynyl
shift.The
final
section
explores
N-electron
polarization
1,3-enynes
enables
chemoselectivity
metal-free
inter-
couplings
indole
substrates.
Our
modulating
conjugation
within
enyne
skeleton─through
linear
cross
conjugation─can
pathways
control
product
selectivity.This
aims
to
stimulate
broader
intermediate-controlled
activated
π-systems.
Future
directions
include
advanced
design,
strategies,
deeper
studies
enable
rational
development.
Язык: Английский
Hydro-phosphorothiolation of Styrene and Cyclopropane with S-Hydrogen Phosphorothioates under Ambient Conditions
Organic Letters,
Год журнала:
2024,
Номер
26(24), С. 5141 - 5145
Опубликована: Июнь 7, 2024
A
metal-free
hexafluoroisopropanol-mediated
hydro-phosphorothiolation
of
styrenes
and
donor-acceptor
cyclopropanes
with
Язык: Английский
Allure of HFIP in Unsaturated Carbon−Carbon Bond Functionalization
European Journal of Organic Chemistry,
Год журнала:
2024,
Номер
27(12)
Опубликована: Фев. 14, 2024
Abstract
Hexafluoroisopropanol
(HFIP)
stands
out
as
a
versatile
solvent
in
synthetic
chemists’
repertoire,
facilitating
diverse
array
of
intricate
chemical
reactions.
It
demonstrates
multifaceted
role
that
extends
beyond
conventional
uses
and,
many
cases,
the
mechanism
appears
to
be
complicated.
This
feature
article
elucidates
significance
HFIP
context
Lewis
and
Brønsted
acid‐catalyzed
reactions
with
specific
emphasis
on
regio‐
stereoselective
functionalization
unsaturated
carbon‐carbon
bonds.
Язык: Английский
H2O ⋅ B(C6F5)3‐Catalyzed para‐Alkylation of Anilines with Alkenes Applied to Late‐Stage Functionalization of Non‐Steroidal Anti‐Inflammatory Drugs
Laura Winfrey,
Yun Lei,
Ginevra Passeri
и другие.
Chemistry - A European Journal,
Год журнала:
2024,
Номер
30(13)
Опубликована: Янв. 15, 2024
Abstract
Anilines
are
core
motifs
in
a
variety
of
important
molecules
including
medicines,
materials
and
agrochemicals.
We
report
straightforward
procedure
that
allows
access
to
new
chemical
space
anilines
via
their
para
‐C−H
alkylation.
The
method
utilizes
commercially
available
catalytic
H
2
O
⋅
B(C
6
F
5
)
3
is
highly
selective
for
‐
C
‐alkylation
(over
N
ortho
C‐
alkylation)
anilines,
with
wide
scope
both
the
aniline
substrates
alkene
coupling
partners.
Readily
alkenes
used,
include
classes
first
time.
mild
reaction
conditions
have
allowed
be
applied
late‐stage‐functionalization
non‐steroidal
anti‐inflammatory
drugs
(NSAIDs),
fenamic
acids
diclofenac.
formed
novel
NSAID
derivatives
display
improved
properties
over
parent
structure.
Язык: Английский
Acetate Assistance in Regioselective Hydroamination of Allenamides: A Combined Experimental and Density Functional Theory Study
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(9), С. 5927 - 5940
Опубликована: Апрель 23, 2024
A
key
factor
in
the
development
of
selective
nucleophilic
addition
to
allenamides
is
controlling
reactivity
electrophilic
intermediates,
which
generally
achieved
using
an
activator
via
conjugated
iminium
intermediates.
In
this
combined
experimental
and
computational
study,
we
show
that
a
general
highly
chemoselective
hydroamination
can
be
accomplished
combination
1,1,1,3,3,3-hexafluoro-2-propanol
(HFIP)
NaOAc.
Experimental
mechanistic
studies
revealed
HFIP
mediates
proton
transfer
activate
allenamide,
while
acetate
additive
significantly
contributes
N-selective
interception.
This
strategy
enables
without
use
metals.
We
demonstrated
various
functionalized
1,3-diamines
could
readily
synthesized
diversified
into
value-added
structural
motifs.
Detailed
investigations
density
functional
theory
role
NaOAc
formation
reactive
ultimately
governed
1,3-diamine
products.
Critically,
calculations
potential
energy
surface
around
proton-transfer
transition
state
two
different
intermediates
were
formed
when
was
added.
Язык: Английский
Hexafluoroisopropanol (HFIP)-Mediated Intramolecular Cyclization of Allenamides To Access C1-Vinyl Tetrahydro-β-carbolines
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(16), С. 11783 - 11788
Опубликована: Июль 26, 2024
The
construction
of
biologically
interesting
N-heterocycles
under
metal-free
conditions
is
a
constant
goal
in
industry
and
academia.
Herein,
we
have
developed
an
hexafluoroisopropanol
(HFIP)-mediated
intramolecular
cyclization
allenamides,
providing
tetrahydro-β-carboline
derivatives
embedded
with
C1-vinyl
functionality.
protocol
provided
atom-efficiently
room
temperature
broad
substrate
scope
good
to
excellent
yields.
potential
impact
the
further
highlighted
by
synthesizing
important
molecules
diversified
scaffolds
via
postsynthetic
modifications.
Язык: Английский
para-Selective C-H Functionalization of Anilines: A Review
Fatemeh Doraghi,
Yasin Mohammadkhani Kalooei,
Negar Mehdi zadeh Darban
и другие.
Journal of Organometallic Chemistry,
Год журнала:
2024,
Номер
1019, С. 123313 - 123313
Опубликована: Авг. 16, 2024
Язык: Английский
HFIP-Mediated Cascade Aminomethylation and Intramolecular Cyclization of Allenamides with N,O-Acetals to Access Tetrahydro-β-carboline Derivatives
Chemical Communications,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
A
cascade
of
two
C–C
bond
forming
reactions
promoted
alone
by
HFIP
is
described
delivering
tetrahydro-β-carboline
derivatives
embedded
with
an
allylic
amine
functionality.
Язык: Английский
Catalyst‐ and Additive‐free, Regioselective 1,6‐Hydroarylation of para‐Quinone Methides with Anilines in HFIP
Chemistry - An Asian Journal,
Год журнала:
2023,
Номер
18(23)
Опубликована: Окт. 17, 2023
A
simple
and
efficient
method
for
the
synthesis
of
diarylmethyl-functionalized
anilines
through
hexafluoroisopropanol
(HFIP)-mediated
regioselective
1,6-hydroarylation
reaction
para-quinone
methides
(p-QMs)
with
under
catalyst-
additive-free
conditions
is
reported.
Various
kinds
p-QMs
amines
(e.
g.
primary,
secondary
tertiary
amines)
are
well
tolerated
in
this
transformation
without
pre-protection
amino
group,
corresponding
products
could
be
generated
good
to
excellent
yields
satisfactory
regioselectivity
optimized
conditions.
In
addition
adaptable
amine
compounds,
indoles
their
derivatives
also
compatible
system.
This
can
easily
extended
a
gram
scale-synthesis
level
synthesize
target
product.
Furthermore,
it
worth
noting
that
some
complex
small
aniline
molecules
biological
activity
selectively
modified
using
method.
The
possible
mechanism
proposed
step-by-step
control
experiments
DFT
calculations,
showing
key
process
achieving
hydrogen
bonding
effect
HFIP
substrates.
Язык: Английский
Ortho-allylation of anilines with vinylaziridines in hexafluoroisopropanol
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 14, 2024
Reaction
of
N
,
-dialkylanilines
with
2-vinylaziridines
in
hexafluoroisopropanol
affords
2-monoallylated
anilines
(
E
)-configured
C–C
double
bonds.
Язык: Английский