ACS Catalysis,
Год журнала:
2021,
Номер
11(6), С. 3755 - 3761
Опубликована: Март 10, 2021
Enantioselective
electrophilic
three-component
thioarylation
of
alkenes
by
chiral
selenide
catalysis
with
free
phenols
as
arylating
sources
is
disclosed.
A
variety
were
achieved
in
high
regio-,
enantio-,
and
diastereoselectivities.
Mechanistic
studies
revealed
that
this
transformation
went
through
carbon
nucleophilic
attack
to
give
the
products
rather
than
process
intramolecular
rearrangement
phenolic
ether
intermediates.
The
application
organocatalytic
method
alkylation
methoxy-substituted
benzenes
elucidated
its
generality.
Chemical Science,
Год журнала:
2021,
Номер
12(32), С. 10686 - 10695
Опубликована: Янв. 1, 2021
Short
aliphatic
groups
are
prevalent
in
bioactive
small
molecules
and
play
an
essential
role
regulating
physicochemistry
molecular
recognition
phenomena.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(10), С. 7029 - 7038
Опубликована: Март 1, 2024
Enantioselective
difunctionalization
of
alkenes
offers
a
straightforward
means
for
the
rapid
construction
enantioenriched
complex
molecules.
Despite
tremendous
efforts
devoted
to
this
field,
enantioselective
aminative
remains
challenge,
particularly
through
an
electrophilic
addition
fashion.
Herein,
we
report
unprecedented
approach
via
copper-catalyzed
with
external
azo
compounds
as
nitrogen
sources.
A
series
valuable
cyclic
hydrazine
derivatives
either
[3
+
2]
cycloaddition
or
intramolecular
cyclization
have
been
achieved
in
high
chemo-,
regio-,
enantio-,
and
diastereoselectivities.
In
transformation,
wide
range
functional
groups,
such
carboxylic
acid,
hydroxy,
amide,
sulfonamide,
aryl
could
serve
nucleophiles.
Importantly,
new
cyano
oxazoline
chiral
ligand
was
found
play
crucial
role
control
enantioselectivity.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
147(9), С. 8024 - 8031
Опубликована: Фев. 20, 2025
Electrocatalytically
selective
chlorination
of
olefins
in
Cl--containing
solutions
is
a
sustainable
method
for
synthesizing
chlorohydrin/vicinal
dichloride;
however,
controlling
the
selectivity
challenging.
Here,
aqueous/dimethyl
carbonate
(DMC)
hybrid
electrolytes
with
different
H2O/DMC
ratios
are
designed
to
modulate
·OH
formation
increase
corresponding
selectivities.
The
combined
results
in/ex
situ
spectroscopies
and
molecular
dynamics
simulations
reveal
origin
high
selectivity.
TFSI-
shields
transportation
free
H2O
provide
moderate
synthesis
chlorohydrin.
DMC
reconstructs
hydrogen
bonds
minimize
interaction
between
them
anode,
matching
requirements
vicinal
dichloride
production.
Thus,
these
not
only
achieve
selectivities
80%
76%
chlorohydrin
dichloride,
respectively,
but
also
enable
other
isolated
yields
up
74%.
This
work
provides
facile
strategy
regulate
anodic
via
rational
electrolyte
design.
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.
Organic & Biomolecular Chemistry,
Год журнала:
2021,
Номер
19(12), С. 2578 - 2602
Опубликована: Янв. 1, 2021
In
this
review
we
target
sp,
sp2and
sp3carbon
fluorination,
chlorination,
bromination
and
iodination
reactions
using
electrolysis
as
a
redox
medium.
Mechanistic
insights
substrate
reactivity
are
also
discussed.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(8), С. 4808 - 4818
Опубликована: Фев. 16, 2023
The
textbook
alkene
halogenation
reaction
establishes
straightforward
access
to
vicinal
dihaloalkanes.
However,
a
robust
catalytic
method
for
dihalogenizing
electron-deficient
olefins
in
an
enantioselective
manner
is
still
under
development,
and
its
mechanism
remains
controversial.
Herein,
we
disclose
efficient
regio-,
anti-diastereo-,
dibromination,
bromochlorination,
dichlorination
reactions
of
enones
catalyzed
by
chiral
N,N'-dioxide/Yb(OTf)3
complex.
With
the
combination
electrophilic
halogen
halide
salts
as
halogenating
agents,
array
homo-
heterodihalogenated
derivatives
achieved
moderate
good
enantioselectivities.
Moreover,
DFT
calculations
reveal
that
novel
triplet
halo-radical
pylon
intermediate
probable
accounting
exclusive
regio-
anti-diastereoselectivity.
Journal of the American Chemical Society,
Год журнала:
2018,
Номер
140(51), С. 17840 - 17845
Опубликована: Дек. 10, 2018
The
biosynthetic
route
to
the
napyradiomycin
family
of
bacterial
meroterpenoids
has
been
fully
described
32
years
following
their
original
isolation
and
11
after
gene
cluster
discovery.
antimicrobial
cytotoxic
natural
products
napyradiomycins
A1
B1
are
produced
using
three
organic
substrates
(1,3,6,8-tetrahydroxynaphthalene,
dimethylallyl
pyrophosphate,
geranyl
pyrophosphate),
catalysis
via
five
enzymes:
two
aromatic
prenyltransferases
(NapT8
T9);
vanadium
dependent
haloperoxidase
(VHPO)
homologues
(NapH1,
H3,
H4).
Building
upon
previous
characterization
NapH1,
T8,
we
herein
describe
initial
(NapT9,
H1)
final
(NapH4)
steps
required
for
construction.
This
remarkably
streamlined
biosynthesis
highlights
utility
VHPO
enzymology
in
complex
product
generation,
as
NapH4
efficiently
performs
a
unique
chloronium-induced
terpenoid
cyclization
establish
stereocenters
new
carbon-carbon
bond,
dual-acting
NapH1
catalyzes
chlorination
etherification
reactions
at
distinct
stages
pathway.
Moreover,
employed
recombinant
enzymes
chemoenzymatically
synthesize
milligram
quantities
one
pot
1
day.
method
represents
viable
enantioselective
approach
produce
halogenated
metabolites,
like
B1,
that
have
yet
be
chemically
synthesized.
ACS Catalysis,
Год журнала:
2018,
Номер
9(1), С. 216 - 223
Опубликована: Ноя. 29, 2018
Transient
dative
substrate–Ti
interactions
have
been
found
to
play
a
key
role
in
controlling
the
regioselectivity
of
alkyne
insertion
and
[2+2]
cycloaddition
Ti-catalyzed
[2+2+1]
pyrrole
synthesis
hydroamination.
TMS-protected
alkynes
with
pendent
Lewis
basic
groups
can
invert
insertion,
leading
selective
formation
highly
substituted
3-TMS
pyrroles.
The
competency
various
potential
directing
was
investigated,
it
that
directing-group
effect
be
tuned
by
modifying
catalyst
acidity,
basicity,
or
tether
length.
Dative
effects
are
unexplored
Ti
catalysts,
this
study
demonstrates
power
substrate-Ti
tuning
selectivity.
