Angewandte Chemie,
Год журнала:
2019,
Номер
132(21), С. 8080 - 8090
Опубликована: Дек. 2, 2019
Abstract
Direct
deprotonation
represents
an
extremely
simple,
straightforward,
and
atom‐economic
strategy
to
activate
pronucleophiles
bearing
acidic
proton.
However,
the
difficulty
often
arises
in
activating
with
high
p
K
a
values
by
using
conventional
chiral
tertiary
amines.
To
overcome
this
challenge,
handful
of
novel
Brønsted
superbases,
including
amidines,
guanidines,
cyclopropenimines,
iminophosphoranes,
have
been
discovered
recent
years.
This
minireview
focuses
on
application
these
organo‐superbases
catalytic
asymmetric
reactions
weakly
pronucleophiles,
highlights
their
comparison
amines,
demonstrating
highly
efficient
processes
stereoselectivity
controlled
conversions
superbases.
The
advantage
new
superbases
brings
great
opportunity
for
developing
more
transformations
pronucleophiles.
European Journal of Organic Chemistry,
Год журнала:
2022,
Номер
26(7)
Опубликована: Дек. 15, 2022
Abstract
Thiourea‐
and
squaramide‐based
bifunctional
base
catalysts
represent
nowadays
a
powerful
tool
in
the
field
of
asymmetric
catalysis
have
demonstrated
very
efficient
for
promoting
wide
variety
transformations
enantioselectively.
New
versions
that
incorporate
one
or
various
additional
H‐bond
donor
site(s)
catalyst
structure
been
developed
recently
which
led
to
more
active
(reduced
loadings)
selective
catalysts.
This
review
highlights
pioneering
ideas
most
recent
contributions
area
with
material
organized
according
nature
functionality.
The
advantages,
current
limitations
perspectives
these
new
multifunctional
are
discussed.
Journal of the American Chemical Society,
Год журнала:
2020,
Номер
142(8), С. 3724 - 3728
Опубликована: Фев. 11, 2020
Recently,
chiral
Brønsted
bases
having
high
basicity
have
emerged
as
a
powerful
tool
in
developing
new
catalytic
enantioselective
reactions.
However,
such
strong
base
catalysts
are
still
very
scarce.
Herein,
we
report
the
development
of
anionic
N,N′-dialkyl
ureate
moiety
basic
site.
Its
prominent
activity
was
demonstrated
addition
reactions
α-thioacetamides
less
acidic
pronucleophiles
with
various
electrophiles.
Thus,
newly
developed
catalyst
accessibility
and
structural
tunability
would
expand
scope
viable
transformations
under
catalysis.
Bulletin of the Chemical Society of Japan,
Год журнала:
2021,
Номер
94(1), С. 339 - 356
Опубликована: Янв. 1, 2021
Abstract
In
this
account,
we
summarized
our
recent
efforts
to
develop
molecular
transformations
under
Brønsted
base
catalysis
on
the
basis
of
own
guiding
principles
for
designing
reaction
systems,
that
include
“the
generation
and
application
anionic
species
which
are
difficult
utilize
in
conventional
systems”
employment
organosuperbases
possessing
much
higher
basicities
than
organic
bases
as
a
catalyst”.
particular,
discussed
reactions
involving
carbanions
less
acidic
compounds
through
formal
umpolung
process
from
carbonyl
[3+2]
cycloadditions
synthetic
equivalent
1,3-dipole
epoxide
opening.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Июнь 20, 2024
The
synthesis
of
chiral
α-azaheteroaryl
oxiranes
via
enantioselective
catalysis
is
a
formidable
challenge
due
to
the
required
complex
stereoselectivity
and
diverse
N-heterocyclic
structures.
These
compounds
play
crucial
role
in
developing
bioactive
molecules,
where
precise
chirality
significantly
influences
biological
activity.
Here
we
show
that
using
phosphoric
acid
as
catalyst,
our
method
efficiently
addresses
these
challenges.
This
technique
not
only
achieves
high
enantio-
diastereoselectivity
but
also
demonstrates
superior
chemo-
stereocontrol
during
epoxidation
alkenyl
aza-heteroarenes.
Our
approach
leverages
synergistic
blend
electrostatic
hydrogen-bonding
interactions,
enabling
effective
activation
both
substrates
hydrogen
peroxide.
resulting
exhibit
enhanced
diversity
functionality,
aiding
construction
azaaryl
with
contiguous
stereocenters.
Kinetic
density
functional
theory
studies
elucidate
mechanism,
highlighting
acid's
pivotal
this
intricate
process.
Angewandte Chemie International Edition,
Год журнала:
2020,
Номер
59(19), С. 7472 - 7477
Опубликована: Фев. 14, 2020
Abstract
In
the
field
of
chiral
Brønsted
base
catalysis,
a
new
generation
catalysts
has
been
highly
anticipated
to
overcome
intrinsic
limitation
pronucleophiles
that
are
applicable
enantioselective
reactions.
Herein,
we
reveal
conceptually
consisting
two
different
organobase
functionalities,
one
which
functions
as
an
organosuperbase
and
other
substrate
recognition
site.
Their
prominent
activity,
stems
from
distinctive
cooperative
function
by
organobases
in
single
catalyst
molecule,
was
demonstrated
unprecedented
direct
Mannich‐type
reaction
α‐phenylthioacetate
less
acidic
pronucleophile.
The
present
achievement
would
provide
guiding
principle
for
design
development
significantly
broaden
utility
catalysis
asymmetric
organic
synthesis.
Chemical Science,
Год журнала:
2021,
Номер
12(17), С. 6064 - 6072
Опубликована: Янв. 1, 2021
The
activation
of
both
aromatic
and
aliphatic
ureas
as
N-centered
nucleophiles
in
intramolecular
Michael
addition
reactions
to
α,β-unsaturated
esters
was
achieved
under
bifunctional
iminophosphorane
squaramide
superbase
catalysis.
ACS Catalysis,
Год журнала:
2022,
Номер
12(15), С. 9611 - 9620
Опубликована: Июль 22, 2022
We
herein
report
the
copper-catalyzed
asymmetric
conjugate
addition
of
β-substituted
alkenyl
heteroarenes,
one
most
challenging
Michael
acceptors,
with
alkenes
as
latent
nucleophiles.
Diverse
chiral
heteroarenes
bearing
two
vicinal
stereocenters
were
obtained
in
good
to
excellent
yields,
generally
enantioselectivity,
and
a
level
diastereoselectivity.
The
products
can
be
readily
transformed
into
other
valuable
acyclic
enantioenriched
structures
three
contiguous
via
amine
catalysis.
Mechanistic
studies,
including
an
isotope
labeling
experiment,
nonlinear
effect
study,
kinetic
experiments,
initial-rate
kinetics
implemented,
experimental
results
indicated
that
hydrocupration
step
might
turnover-limiting
step.
Moreover,
origin
preferential
alkene
presence
Ph-BPE-ligated
CuH
catalyst
was
also
elucidated
some
control
experiments.
Angewandte Chemie International Edition,
Год журнала:
2020,
Номер
59(40), С. 17417 - 17422
Опубликована: Июнь 19, 2020
A
bifunctional
iminophosphorane
(BIMP)-catalysed
enantioselective
synthesis
of
α,β-unsaturated
cyclohexenones
through
a
facially
selective
1,3-prototropic
shift
β,γ-unsaturated
prochiral
isomers,
under
mild
reaction
conditions
and
in
short
times,
on
range
structurally
diverse
substrates,
is
reported.
α,β-Unsaturated
cyclohexenone
products
primed
for
downstream
derivatisation
were
obtained
high
yields
(up
to
99
%)
consistently
enantioselectivity
%
ee).
Computational
studies
into
the
mechanism
origins
enantioselectivity,
including
multivariate
linear
regression
TS
energy,
carried
out
data
found
be
good
agreement
with
experimental
findings.
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
60(46), С. 24573 - 24581
Опубликована: Сен. 6, 2021
Herein
we
report
an
organocatalytic
enantioselective
functionalization
of
heterocyclic
carboxaldehydes
via
the
Pictet-Spengler
reaction.
Through
careful
pairing
novel
squaramide
and
Brønsted
acid
catalysts,
our
method
tolerates
a
breadth
heterocycles,
enabling
preparation
series
heterocycle
conjugated
β-(tetrahydro)carbolines
in
good
yield
enantioselectivity.
Careful
selection
carboxylic
co-catalyst
is
essential
for
toleration
variety
regioisomeric
heterocycles.
Utility
demonstrated
three-step
stereoselective
pyridine-containing
analogues
potent
selective
estrogen
receptor
downregulator
U.S.
FDA
approved
drug
Tadalafil.
The Chemical Record,
Год журнала:
2023,
Номер
23(7)
Опубликована: Янв. 3, 2023
Abstract
The
sulfa‐Michael
addition
reaction
is
a
crucial
subset
of
the
Michael
reaction,
and
aroused
interest
numerous
synthetic
biologists
chemists.
In
particular,
triggered
cascade
has
developed
quickly
in
recent
years
because
it
offers
an
efficient
method
to
construct
C−S
bonds
other
one
approach,
which
widely
applicable
for
building
chiral
pharmaceuticals,
their
intermediates,
natural
compounds.
This
review
emphasizes
advancements
addition‐triggered
reactions
stereoselective
synthesis
sulfur‐containing
compounds,
including
sulfa‐Michael/aldol,
sulfa‐Michael/Henry,
sulfa‐Michael/Michael,
sulfa‐Michael/Mannich
some
multi‐step
processes.
Moreover,
mechanisms
derivatization
experiments
are
introduced
appropriately.