Organic Letters,
Год журнала:
2018,
Номер
20(20), С. 6384 - 6388
Опубликована: Сен. 28, 2018
Chiral
selenide-catalyzed
oxytrifluoromethylthiolation
of
aliphatic
internal
alkenes
by
a
formally
intermolecular
strategy
is
disclosed,
affording
CF3S
1,3-amino
alcohol
and
1,3-diol
derivatives
with
high
regio-,
enantio-,
diastereoselectivities.
The
reactions
are
promoted
neighboring
imide
or
ester
group
on
substrates
via
six-membered
ring
transition
state.
This
assistance
also
successfully
applied
to
the
regio-
diastereoselective
oxyhalofunctionalization
conversion
alkynes.
Angewandte Chemie International Edition,
Год журнала:
2020,
Номер
59(45), С. 19796 - 19819
Опубликована: Май 26, 2020
The
last
decade
has
witnessed
a
burgeoning
of
new
methods
for
the
enantioselective
vicinal
difunctionalization
alkenes
initiated
by
electrophilic
sulfenyl
group
transfer.
addition
sulfenium
ions
to
results
in
generation
chiral,
non-racemic
thiiranium
ions.
These
highly
reactive
intermediates
are
susceptible
attack
myriad
nucleophiles
stereospecific
ring-opening
event
afford
anti
1,2-sulfenofunctionalized
products.
practical
application
ion
transfer
been
enabled
advances
field
Lewis
base
catalysis.
This
Review
will
chronicle
initial
discovery
and
characterization
followed
determination
their
configurational
stability
challenges
developing
variants.
Once
framework
reactivity
established,
critical
analysis
pioneering
studies
be
presented.
Finally,
comprehensive
discussion
modern
synthetic
applications
categorized
around
type
nucleophile
employed
sulfenofunctionalization.
Nature Communications,
Год журнала:
2021,
Номер
12(1)
Опубликована: Июнь 23, 2021
Abstract
Electrophilic
halogenation
reactions
have
been
a
reliable
approach
to
accessing
organohalides.
During
the
past
decades,
various
catalytic
systems
developed
for
activation
of
haleniums.
However,
there
is
still
short
effective
catalysts,
which
could
cover
and
broad
scope
unsaturated
compounds.
Herein,
TEMPO
(2,2,6,6-tetramethylpiperidine
nitroxide)
its
derivatives
are
disclosed
as
active
catalysts
electrophilic
olefins,
alkynes,
aromatics.
These
stable,
readily
available,
reactive
enough
activate
haleniums
including
Br
+
,
I
even
Cl
reagents.
This
system
applicable
halogenations
haloarylation
olefins
or
dibromination
were
rarely
realized
in
previous
Lewis
base
catalysis
acid
catalysis.
The
high
ability
attributed
synergistic
model
halogenating
reagents,
where
carbonyl
group
halogen
atom
both
activated
by
present
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(7), С. 2943 - 2952
Опубликована: Фев. 10, 2022
Enantioselective
synthesis
of
axially
chiral
sulfur-containing
biaryl
derivatives
through
the
electrophilic
sulfenylation
phenols
has
been
achieved
for
first
time.
This
catalytic
asymmetric
system,
which
involves
sequential
desymmetrization
and
kinetic
resolution,
is
enabled
by
a
combination
novel
3,3'-disubstituted
BINOL-derived
selenide
catalyst
an
achiral
sulfonic
acid.
Control
experiments
computational
studies
suggest
that
multiple
noncovalent
interactions
between
cocatalysts
substrate,
especially
network
hydrogen
bond
interactions,
play
crucial
role
in
determining
enantioselectivity
reactivity.
Organic Chemistry Frontiers,
Год журнала:
2022,
Номер
9(23), С. 6684 - 6707
Опубликована: Янв. 1, 2022
This
review
systematically
summarizes
the
recent
developments
for
constructing
sulfur
compounds
from
electrophiles,
and
mechanism
mainly
involved
thirranium
ions,
ylides,
C–S
cross
coupling
electrophilic
substitution.
Chemical Society Reviews,
Год журнала:
2023,
Номер
53(2), С. 586 - 605
Опубликована: Дек. 7, 2023
Catalysts
play
a
major
role
in
chemical
synthesis,
and
catalysis
is
considered
to
be
green
economic
process.
Catalysis
dominated
by
covalent
interactions
between
the
catalyst
substrate.
The
design
of
non-covalent
catalysts
came
into
limelight
only
recently.
Hydrogen
bonding
(HB)
are
well
established
among
catalysts,
including
asymmetric
HB
catalysts.
Though
halogen
(XB)
its
version
gaining
admiration,
chalcogen
(ChB)
budding
stage.
This
tutorial
review
will
focus
on
recently
evolved
emphasis
given
chiral
molecules.
Since
successful
enantioselective
yet
reported,
this
basics
catalysis,
chalcogenide
rigidification
transition
states
ChB,
stabilization
cations
chalcogens,
details
unsuccessful
enantioseparation
racemic
molecules
using
existence
ChB
biomolecules.
ACS Organic & Inorganic Au,
Год журнала:
2024,
Номер
4(3), С. 287 - 300
Опубликована: Март 4, 2024
In
the
past
5
years,
hexafluoroisopropanol
(HFIP)
has
been
used
as
a
unique
solvent
or
additive
to
enable
challenging
transformations
through
substrate
activation
and
stabilization
of
reactive
intermediates.
this
Review,
we
aim
at
describing
difunctionalization
processes
which
were
unlocked
when
HFIP
was
involved.
Specifically,
focus
on
cyclizations
additions
alkenes,
alkynes,
epoxides,
carbonyls
that
introduce
wide
range
functional
groups
interest.
ACS Catalysis,
Год журнала:
2024,
Номер
14(8), С. 6009 - 6015
Опубликована: Апрель 5, 2024
Rhodium(III)-catalyzed
atroposelective
C–H
selenylation
of
1-aryl
isoquinolines
has
been
achieved.
The
direct
reaction
between
and
2-(phenylselanyl)isoindoline-1,3-dione
in
the
presence
chiral
SCpRh(III)
complex
afforded
a
series
axially
isoquinoline
selenides
up
to
95%
yield
96%
ee.
features
mild
conditions
broad
substrate
scope.
DFT
calculations
revealed
that
C–Se
bond
formation
step
proceeds
through
formal
SN2
pathway.
ACS Catalysis,
Год журнала:
2018,
Номер
8(7), С. 6745 - 6750
Опубликована: Июнь 19, 2018
Unprecedented
selenium-catalyzed
propargylic
oxidation
of
alkynes
is
disclosed.
Various
propargylphosphonates
and
3-alkynoates
were
efficiently
converted
to
valuable
ynones
via
unusual
C–C
triple
bond
migration
deselenenylation
at
a
vinyl
carbon.
By
the
strategies
tautomerization
enamine
intermediate
SN2
displacement,
similar
conditions
effective
for
oxidative
difunctionalization
ynamides
afford
multisubstituted
oxazoles
with
high
regioselectivity.
Mechanistic
studies
revealed
these
detailed
processes.
Angewandte Chemie International Edition,
Год журнала:
2019,
Номер
58(36), С. 12491 - 12496
Опубликована: Июль 11, 2019
An
enantioselective
sulfenylation/semipinacol
rearrangement
of
1,1-disubstituted
and
trisubstituted
allylic
alcohols
was
accomplished
with
a
chiral
Lewis
base
Brønsted
acid
as
cocatalysts,
generating
various
β-arylthio
ketones
bearing
an
all-carbon
quaternary
center
in
moderate
to
excellent
yields
enantioselectivities.
These
arylthio
ketone
products
are
common
intermediates
many
applications,
for
example,
the
design
new
catalysts/ligands
total
synthesis
natural
products.
Computational
studies
(DFT
calculations)
were
carried
out
explain
enantioselectivity
role
acid.
Additionally,
synthetic
utility
this
method
exemplified
by
(-)-herbertene
one-pot
sulfoxide
sulfone.
Journal of the American Chemical Society,
Год журнала:
2019,
Номер
141(35), С. 13767 - 13771
Опубликована: Авг. 21, 2019
A
method
for
the
catalytic,
enantioselective,
intermolecular,
1,2-sulfenoamination
of
alkenes
is
described.
Functionalization
achieved
through
intermediacy
an
enantioenriched,
configurationally
stable
thiiranium
ion
generated
by
Lewis
base
activation
a
readily
available
sulfur
electrophile.
diverse
set
anilines
and
benzylamines
react
with
different
styrenes
to
afford
products
in
good
yield
stereoselectivity.
Downstream
manipulation
facilitated
deprotonation
amines
enable
carbon–sulfur
bond
cleavage.