The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 14, 2025
An
efficient
method
for
copper-catalyzed
asymmetric
protoboration
of
allenyl
sulfones
with
bis(pinacolato)diboron
was
developed,
providing
chiral
allylic
high
efficiency
and
excellent
enantioselectivity.
Notably,
the
directing
effect
sulfone
group
plays
a
pivotal
role
in
achieving
both
regioselectivity
Journal of the American Chemical Society,
Journal Year:
2021,
Volume and Issue:
143(19), P. 7285 - 7291
Published: May 10, 2021
Herein
we
describe
a
protocol
for
the
unprecedented
stereodivergent
synthesis
of
tertiary
fluoride-tethered
allenes
bearing
stereogenic
center
and
axis
via
Cu/Pd
synergistic
catalysis.
A
broad
scope
conjugated
enynes
are
coupled
with
various
α-fluoroesters
in
high
yields
diastereoselectivities
generally
>99%
ee.
In
addition,
four
stereoisomers
allene
products
ensure
precise
access
to
corresponding
fluorinated
hydrofurans
novel
axial-to-central
chirality
transfer
process.
ACS Catalysis,
Journal Year:
2021,
Volume and Issue:
11(7), P. 4169 - 4204
Published: March 19, 2021
Arylsulfonyl
compounds
are
among
the
most
important
in
pharmaceutical
and
medicinal
chemistry.
Hence,
a
wide
variety
of
sulfonylation
methods
have
been
reported
recently.
This
review
summarizes
arylsulfonylation
methodologies
developed
last
5
years
includes
two
major
categories.
The
first
entails
direct
second
multicomponent
arylsulfonylation.
In
arylsulfonylation,
arylsulfonyl
reagents
react
with
C–H
activated
compounds,
alkynes,
alkenes
through
coupling
or
addition
reactions.
reactions,
arylation
various
substrates
sulfur
dioxide
surrogates,
such
as
DABSO,
Na2S2O5,
K2S2O5.
hydrazides,
aryl
boronic
acids,
silanes,
halides
widely
employed
that
surrogates
to
generate
an
source,
ensuing
reactions
proceed
via
pathways
analogous
those
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(7), P. 3915 - 3925
Published: Feb. 10, 2023
The
straightforward
construction
of
stereogenic
centers
bearing
unprotected
functional
groups,
as
in
nature,
has
been
a
persistent
pursuit
synthetic
chemistry.
Abundant
applications
free
enantioenriched
allyl
alcohol
and
hydroxylamine
motifs
have
made
the
asymmetric
hydration
hydroaminoxylation
conjugated
dienes
from
water
hydroxylamine,
respectively,
intriguing
efficient
routes
that
have,
however,
unachievable
thus
far.
A
fundamental
challenge
is
failure
to
realize
transition-metal-catalyzed
enantioselective
C–O
bond
constructions
via
hydrofunctionalization
dienes.
Here,
we
perform
comprehensive
study
toward
stereoselective
formal
by
synthesizing
set
new
P,N-ligands
identifying
an
aryl-derived
oxime
surrogate
for
both
hydroxylamine.
Asymmetric
hydroalkoxylation
with
also
elucidated.
Furthermore,
versatile
derivatizations
following
provide
indirect
but
concise
hydrophenoxylation,
hydrofluoroalkoxylation,
hydrocarboxylation
unreported
Finally,
ligand-to-ligand
hydrogen
transfer
process
proposed
based
on
results
preliminary
mechanistic
experiments.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(4), P. 2748 - 2756
Published: Jan. 12, 2024
Controlling
the
enantioselectivity
of
hydrogen
atom
transfer
(HAT)
reactions
has
been
a
long-standing
synthetic
challenge.
While
recent
advances
on
photoenzymatic
catalysis
have
demonstrated
great
potential
non-natural
photoenzymes,
all
transformations
are
initiated
by
single-electron
reduction
substrate,
with
only
one
notable
exception.
Herein,
we
report
an
oxidation-initiated
enantioselective
hydrosulfonylation
olefins
using
novel
mutant
gluconobacter
ene-reductase
(GluER-W100F-W342F).
Compared
to
known
systems,
our
approach
does
not
rely
formation
electron
donor–acceptor
complex
between
substrates
and
enzyme
cofactor
simplifies
reaction
system
obviating
addition
regeneration
mixture.
More
importantly,
GluER
variant
exhibits
high
reactivity
broad
substrate
scope.
Mechanistic
studies
support
proposed
mechanism
reveal
that
tyrosine-mediated
HAT
process
is
involved.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(5), P. 3725 - 3732
Published: Feb. 21, 2024
The
chiral
allylic
sulfonylated
group
is
a
unique
structural
motif
embedded
in
range
of
natural
products
and
pharmaceuticals.
Notably,
the
synthesis
structurally
diverse
derivatives
via
alkylsulfonylation
1,3-dienes
remains
underexplored
because
its
inherent
challenges
stereocontrol
regioselectivity.
Herein,
photoinduced,
palladium-catalyzed
enantioselective
1,2-alkylsulfonylation
conjugated
described.
A
wide
variety
alkyl
bromides,
1,3-dienes,
sodium
sulfinates
could
be
facilely
coupled
to
generate
value-added
with
high
enantioselectivity.
Finally,
utility
this
difunctionalization
protocol
was
demonstrated
pharmaceutical
analogue
synthesis.
Journal of the American Chemical Society,
Journal Year:
2021,
Volume and Issue:
143(16), P. 6176 - 6184
Published: April 15, 2021
In
this
article,
we
advance
Rh-catalyzed
hydrothiolation
through
the
divergent
reactivity
of
cyclopropenes.
Cyclopropenes
undergo
to
provide
cyclopropyl
sulfides
or
allylic
sulfides.
The
choice
bisphosphine
ligand
dictates
whether
pathway
involves
ring-retention
ring-opening.
Mechanistic
studies
reveal
origin
for
switchable
selectivity.
Our
results
suggest
two
pathways
share
a
common
cyclopropyl-Rh(III)
intermediate.
Electron-rich
Josiphos
ligands
promote
direct
reductive
elimination
from
intermediate
afford
in
high
enantio-
and
diastereoselectivities.
Alternatively,
atropisomeric
(such
as
DTBM-BINAP)
enable
ring-opening
generate
with
regiocontrol.
Angewandte Chemie International Edition,
Journal Year:
2021,
Volume and Issue:
60(15), P. 8321 - 8328
Published: Jan. 19, 2021
Abstract
Depending
on
the
reactant
property
and
reaction
mechanism,
one
major
regioisomer
can
be
favored
in
a
that
involves
multiple
active
sites.
Herein,
an
orthogonal
regulation
of
nucleophilic
electrophilic
sites
regiodivergent
hydroamination
isoprene
with
indazoles
is
demonstrated.
Under
Pd‐hydride
catalysis,
1,2‐
or
4,3‐insertion
pathway
respect
to
could
controlled
by
choice
ligands.
In
terms
indazoles,
occurs
at
either
N
1
‐
2
‐position
governed
acid
co‐catalysts.
Preliminary
experimental
studies
have
been
performed
rationalize
mechanism
regioselectivity.
This
study
not
only
contributes
practical
tool
for
selective
functionalization
isoprene,
but
also
provides
guide
manipulate
regioselectivity
‐functionalization
indazoles.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(25), P. 11364 - 11376
Published: June 10, 2022
Pd-catalyzed
sequential
hydroamination
of
readily
available
1,3-enynes
is
reported.
The
redox-neutral
process
provides
an
efficient
route
to
synthesize
a
broad
scope
imidazolidinones,
thiadiazolidines,
and
imidazolidines.
Asymmetric
generates
series
synthetically
valuable,
enantioenriched
imidazolidinones.
Mechanistic
studies
revealed
that
the
transformation
occurred
via
intermolecular
enyne
pathway
give
allene
intermediate.
Subsequent
intramolecular
intermediate
proceeded
under
Curtin-Hammett
principle
provide
imidazolidinone
products.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(7), P. 3909 - 3914
Published: Feb. 10, 2023
As
an
advance
in
hydrofunctionalization,
we
herein
report
that
alcohols
add
to
1,3-dienes
with
high
regio-
and
enantioselectivity.
Using
Ni-DuPhos,
access
enantioenriched
allylic
ethers.
Through
the
choice
of
solvent-free
conditions,
control
reversibility
C–O
bond
formation.
This
work
showcases
a
rare
example
methanol
as
reagent
asymmetric
synthesis.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(52)
Published: Nov. 13, 2023
Impressive
progress
has
been
made
in
the
copper-catalyzed
asymmetric
propargylic
substitution
(APS)
reaction,
but
its
use
remote
yne-allylic
remains
a
challenging
topic.
Herein,
we
report
first
enantioselective
sulfonylation
of
esters
with
sodium
sulfinates.
The
reaction
is
assumed
to
occur
via
copper-vinylvinylidene
species
as
key
reactive
intermediate.
readily
available
starting
materials,
mild
conditions,
and
excellent
regio-,
enantio-
stereoselectivity,
well
broad
substrate
scope
(>70
examples),
show
practicality
attractiveness
this
method.