ACS Catalysis,
Год журнала:
2021,
Номер
11(15), С. 9271 - 9278
Опубликована: Июль 12, 2021
To
date,
numerous
methods
have
been
successfully
developed
to
functionalize
N-heteroaryl
C–H
bonds.
In
contrast,
dearomative
tandem
functionalization
of
N-heteroarenes
is
still
a
subject
be
explored.
Reported
herein
an
example
on
reductive
dearomatization-induced
by
ruthenium
catalysis,
which
offers
general
method
for
diastereoselective
construction
fused
heterocycles
featuring
cyclic
syn-N,
O-acetal
motif
from
N-heteroarenes,
phenols,
and
paraformaldehyde.
Mechanistic
study
reveals
that
the
products
are
formed
via
sequence
pyridyl
C3-benzylation
hydroxymethylation
followed
C2-aryloxylation
N-heteroarenium
salts,
proceeding
with
broad
substrate
scope,
good
functional
group
tolerance,
high
atom
efficiency,
applicability
postfunctionalization
some
biomedical
molecules.
Chemical Reviews,
Год журнала:
2018,
Номер
119(3), С. 1855 - 1969
Опубликована: Дек. 24, 2018
In
this
review,
we
summarize
the
origin
and
advancements
of
iridium-catalyzed
asymmetric
allylic
substitution
reactions
during
past
two
decades.
Since
first
report
in
1997,
Ir-catalyzed
have
attracted
intense
attention
due
to
their
exceptionally
high
regio-
enantioselectivities.
been
significantly
developed
recent
years
many
respects,
including
ligand
development,
mechanistic
understanding,
substrate
scope,
application
synthesis
complex
functional
molecules.
an
explicit
outline
ligands,
mechanism,
scope
nucleophiles,
applications
is
presented.
Chemical Society Reviews,
Год журнала:
2018,
Номер
47(15), С. 5946 - 5996
Опубликована: Янв. 1, 2018
In
this
review
we
summarize
the
latest
developments
in
enantioselective
synthesis
of
spirocompounds.
The
most
important
organometallic
and
organocatalytic
methodologies
are
highlighted.
Chemical Society Reviews,
Год журнала:
2018,
Номер
47(11), С. 3831 - 3848
Опубликована: Янв. 1, 2018
This
tutorial
review
provides
a
good
introduction
to
spirocyclization
reactions
of
indole
derivatives
and
highlights
the
recent
advances
in
construction
spiroindolines
spiroindoles.
Journal of the American Chemical Society,
Год журнала:
2018,
Номер
140(6), С. 2080 - 2084
Опубликована: Янв. 30, 2018
We
describe
a
fully
stereodivergent
synthesis
of
range
α,α-disubstituted
α-amino
acids
via
an
Ir/Cu-catalyzed
α-allylation
readily
available
imine
esters.
The
introduction
Cu-Phox
complex-activated
ester
into
the
chiral
iridium-catalyzed
allylic
allylation
process
is
crucial
for
its
high
reactivity
and
excellent
enantio-
diastereoselectivity
(up
to
>99%
ee
>20:1
dr).
Importantly,
two
catalysts
allow
full
control
over
configuration
stereocenters,
affording
all
stereoisomers
desired
products.
utility
this
methodology
was
demonstrated
by
synthesizing
dipeptides
analogues
bioactive
molecules
in
manner.
ACS Central Science,
Год журнала:
2021,
Номер
7(3), С. 432 - 444
Опубликована: Фев. 22, 2021
Asymmetric
catalysis
has
been
recognized
as
the
most
enabling
strategy
for
accessing
chiral
molecules
in
enantioenriched
forms.
Catalytic
asymmetric
dearomatization
is
an
emerging
and
dynamic
research
subject
catalysis,
which
received
considerable
attention
recent
years.
The
direct
transformations
from
readily
available
aromatic
feedstocks
to
structurally
diverse
three-dimensional
polycyclic
make
catalytic
reactions
of
broad
interest
both
organic
synthesis
medicinal
chemistry.
However,
inherent
difficulty
disruption
aromaticity
demands
a
large
energy
input
during
process,
might
be
incompatible
with
conditions
generally
required
by
catalysis.
In
this
Outlook,
we
will
discuss
representative
strategies
examples
various
compounds
try
convince
readers
that
overcoming
above
obstacles,
could
advance
chemical
sciences
many
respects.
ACS Catalysis,
Год журнала:
2019,
Номер
9(3), С. 1820 - 1882
Опубликована: Янв. 31, 2019
The
catalytic
enantioselective
assembly
of
spirocyclic
molecules
featuring
a
spiro
quaternary
carbon
stereocenter
is
currently
great
interest
because
such
privileged
3D
structures
are
widely
present
in
natural
products
that
exhibit
broad
spectrum
biological
and
pharmacological
activities.
This
review
summarizes
the
advances
based
on
six
major
synthetic
strategies
showcases
reaction
mechanisms
detail.
advantages
limitations
each
strategy
presented,
remaining
opportunities
outlined.
Journal of the American Chemical Society,
Год журнала:
2018,
Номер
140(4), С. 1239 - 1242
Опубликована: Янв. 10, 2018
We
report
stereodivergent
allylic
substitution
reactions
of
esters
with
prochiral
enolates
derived
from
azaaryl
acetamides
and
acetates
to
form
products
addition
the
at
most
substituted
carbon
an
allyl
moiety
two
catalysts,
a
chiral
metallacyclic
iridium
complex
bisphosphine-ligated
copper(I)
complex,
which
individually
control
configuration
electrophilic
nucleophilic
atoms,
respectively.
By
simple
permutations
enantiomers
all
four
stereoisomers
containing
stereogenic
centers
were
synthesized
high
diastereoselectivity
enantioselectivity.
A
variety
bearing
pyridyl,
benzothiazolyl,
benzoxazolyl,
pyrazinyl,
quinolinyl
isoquinolinyl
moieties
found
be
suitable
for
this
transformation.
Organic Chemistry Frontiers,
Год журнала:
2020,
Номер
7(23), С. 3967 - 3998
Опубликована: Янв. 1, 2020
This
review
summarizes
the
progresses
in
organocatalytic
asymmetric
dearomatization
reactions
of
indole
derivatives
and
their
applications
total
synthesis
natural
products,
gives
some
insights
into
challenging
issues
this
research
field.
ACS Catalysis,
Год журнала:
2023,
Номер
13(14), С. 9442 - 9475
Опубликована: Июль 3, 2023
Spirocyclic
indole
derivatives
are
fascinating
tridimensional
molecular
scaffolds
from
both
a
synthetic
and
biological
point
of
view.
Among
the
many
strategies
developed
to
access
these
structures,
transition
metal
catalysis
has
recently
led
impressive
advances,
especially
relying
on
unique
reactivity
dearomatized
spirocyclic
intermediates.
These
species
can
indeed
evolve
toward
or
nonspirocyclic
products
through
rearomatization-driven
processes,
which
at
same
time
highly
challenging
control
but
also
source
large
structural
diversity.
This
review
highlights
most
prominent
methods
past
decade
that
involve
spirocyclization
tethered
functional
group
may
be
activated
by
metal,
leading
rearomatized
products.
The
discussion
is
particularly
focused
spiroindoleninium
intermediate
complex
mechanistic
features
regarding
its
evolution,
dependent
catalytic
systems.
