ACS Catalysis,
Год журнала:
2021,
Номер
11(19), С. 12375 - 12383
Опубликована: Сен. 22, 2021
The
Rh(III)-catalyzed
reaction
of
aniline
derivatives
that
contain
a
pyrimidine
directing
group
with
vinylsilanes
results
in
the
formation
C3-substituted
indoline
highly
regioselective
manner
via
C–H
activation/alkene
cyclization
cascade.
mechanistic
experiments
indicate
bond
cleavage
is
not
rate-determining
step
and
proceeds
six-membered
rhodacycle
as
key
catalytic
species
through
pyrimidine-directed
electrophilic
ortho-C–H
rhodation.
Journal of the American Chemical Society,
Год журнала:
2021,
Номер
143(34), С. 13962 - 13970
Опубликована: Авг. 20, 2021
An
alcohol-directed,
nickel-catalyzed
three-component
umpolung
carboamination
of
unactivated
alkenes
with
aryl/alkenylboronic
esters
and
electrophilic
aminating
reagents
is
reported.
This
transformation
enabled
by
specifically
tailored
O-(2,6-dimethoxybenzoyl)hydroxylamine
electrophiles
that
suppress
competitive
processes,
including
undesired
β-hydride
elimination
transesterification
between
the
alcohol
substrate
electrophile.
The
reaction
delivers
desired
1,2-carboaminated
products
generally
high
regio-
syn-diastereoselectivity
exhibits
a
broad
scope
coupling
partners
alkenes,
complex
natural
products.
Various
mechanistic
experiments
analysis
stereochemical
outcome
cyclic
alkene
substrate,
as
confirmed
X-ray
crystallographic
analysis,
support
alcohol-directed
syn-insertion
an
organonickel(I)
species.
ACS Catalysis,
Год журнала:
2022,
Номер
12(7), С. 3890 - 3896
Опубликована: Март 14, 2022
A
versatile
method
to
access
differentially
substituted
1,3-
and
1,4-diamines
via
nickel-catalyzed
three-component
1,2-carboamination
of
alkenyl
amines
with
aryl/alkenylboronic
ester
nucleophiles
N–O
electrophiles
is
reported.
The
reaction
proceeds
efficiently
free
primary
secondary
without
needing
a
directing
auxiliary
or
protecting
group
enabled
by
fine-tuning
the
leaving
on
reagent.
transformation
highly
regioselective
compatible
wide
range
coupling
partners
amine
substrates,
all
performed
at
room
temperature.
series
kinetic
studies
support
mechanism
in
which
alkene
coordination
nickel
catalyst
turnover-limiting.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(21), С. 14521 - 14527
Опубликована: Май 14, 2024
Herein,
the
development
of
a
light-mediated
synthesis
functionalized
indolines
and
tetrahydroquinolines
is
reported.
These
structural
motifs
are
considered
as
highly
valuable
targets,
attributed
to
their
widespread
occurrence
in
pharmaceuticals
natural
products.
The
gold-mediated
approach
offers
direct
route
yields
up
81%
under
mild
photochemical
conditions.
Thereby,
easily
accessible
Boc-protected
N-aryl-allylamine
homoallylamine
derivatives
were
reacted
with
sp3-hybridized
haloalkanes
an
intermolecular
cascade
cyclization
reaction.
A
broad
scope
substrates,
including
variety
different
substituents
on
aromatic
backbone
well
various
haloalkanes,
could
be
utilized.
Indoline
derivatives,
which
position
2,
also
by
applying
ortho-allylic
anilines.
Moreover,
synthetic
appeal
was
demonstrated
for
total
anti-inflammatory
agent
AN669
three
reaction
steps
overall
yield
64%.
Asian Journal of Organic Chemistry,
Год журнала:
2021,
Номер
10(12), С. 3201 - 3232
Опубликована: Ноя. 5, 2021
Abstract
Olefins
are
synthetically
useful
building
blocks
in
modern
organic
synthesis.
Direct
functionalization
of
olefins;
represent
one
the
most
explored
transformations
synthetic
chemistry
due
to
their
easy
availability
and
reactivity
towards
large
number
reactants
affording
diverse
range
compounds.
In
recent
times,
development
new
protocols
for
olefins
is
a
growing
realm.
A
plethora
olefin
methodologies
have
been
reported
literature
through
ionic
free
radical
mechanisms
including
single
electron
transfer
(SET)
last
two
decades.
This
review
gives
an
overview
mono‐
difunctionalization
unactivated
olefins,
with
emphasis
on
mechanistic
details.
Chemical Communications,
Год журнала:
2023,
Номер
59(33), С. 4872 - 4890
Опубликована: Янв. 1, 2023
Recent
advances
in
the
direct
synthesis
of
trifluoromethyl-containing
heterocycles
from
trifluoroacetimidoyl
chlorides
(TFAICs)
and
derivatives,
including
trifluoroacetimidohydrazides
(TFAIHs)
CF3-imidoyl
sulfoxonium
ylides
(TFISYs),
are
systematically
summarized
discussed.
The
cascade
annulation
reactions
synthons
with
suitable
coupling
partners
have
emerged
as
a
powerful
promising
tool
for
construction
variety
trifluoromethyl-substituted
heterocycles.
Compared
other
building
blocks,
TFAICs
derivatives
notable
merits
easy
availability
handling,
relative
stability
safety,
high
reactivity.
Chemical Communications,
Год журнала:
2021,
Номер
57(62), С. 7610 - 7624
Опубликована: Янв. 1, 2021
Palladium
has
proven
to
be
effective
in
catalyzing
the
(hetero)annulation
of
C[double
bond,
length
as
m-dash]C
bonds
with
ambiphilic
organo(pseudo)halides.
Through
employment
appropriate
coupling
partners,
efficient
annulation
a
variety
allenes,
1,3-dienes,
strained
alkenes,
styrenes,
and
other
bond
variants
can
achieved
provide
direct
access
numerous
useful
hetero-
carbocyclic
scaffolds.
In
this
Feature
Article,
we
summarize
palladium-catalyzed
methods
reported
since
2005
(spanning
just
over
15
years)
discuss
outstanding
challenges
area
study.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(13)
Опубликована: Янв. 10, 2022
In
this
study,
we
systematically
evaluate
different
ambiphilic
organohalides
for
their
ability
to
participate
in
anti-selective
carbo-
or
heteroannulation
with
non-conjugated
alkenyl
amides
under
Pd
Chemical Science,
Год журнала:
2022,
Номер
13(12), С. 3526 - 3532
Опубликована: Янв. 1, 2022
The
synthesis
of
diverse
products
from
the
same
starting
materials
is
always
attractive
in
organic
chemistry.
Here,
a
palladium-catalyzed
substrate-controlled
regioselective
functionalization
unactivated
alkenes
with
trifluoroacetimidoyl
chlorides
has
been
developed,
which
provides
direct
but
controllable
access
to
variety
structurally
trifluoromethyl-containing
indoles
and
indolines.
In
more
detail,
respect
γ,δ-alkenes,
1,1-geminal
difunctionalization
chloride
enables
[4
+
1]
annulation
produce
indoles;
as
for
β,γ-alkenes,
[3
2]
heteroannulation
hydrolysis
product
through
1,2-vicinal
occurs
deliver
indoline
products.
structure
alkene
substrates
differentiates
regioselectivity
reaction.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(35), С. 24503 - 24514
Опубликована: Авг. 22, 2024
A
facile
approach
to
obtaining
densely
functionalized
cyclopropanes
is
described.
The
reaction
proceeds
under
mild
conditions
via
the
directed
nucleopalladation
of
nonconjugated
alkenes
with
readily
available
pronucleophiles
and
gives
excellent
yields
good
anti-selectivity
using
I2
TBHP
as
oxidants.
Pronucleophiles
bearing
a
diverse
collection
electron-withdrawing
groups,
including
−CN,
−CO2R,
−COR,
−SO2Ph,
−CONHR,
−NO2,
are
well
tolerated.
Internal
alkenes,
which
generally
challenging
substrates
in
other
cyclopropanation
methods,
provide
diastereoselectivity
this
methodology,
allowing
for
controlled
access
substituted
at
all
three
C
atoms.
DFT
calculations
mechanistic
experiments
reveal
that
major
pathway
involves
initial
α-iodination
nucleophile,
followed
by
anti-carbopalladation
intramolecular
C(sp3)–I
oxidative
addition.
Strain-release-promoted
C(sp3)–C(sp3)
reductive
elimination
then
furnishes
cyclopropanated
product.
