Angewandte Chemie,
Год журнала:
2022,
Номер
134(31)
Опубликована: Май 10, 2022
Abstract
Die
stereospezifische
[1,5]‐Kohlenstoffverschiebung
der
C3‐Ammoniumenolate
wird
beschrieben.
Gemäß
mechanistischen,
kinetischen
und
rechnergestützten
Experimenten
verläuft
die
neuartige
Umlagerung
über
ein
transientes
C3‐Ammoniumenolat.
Dies
durch
eine
katalysierte
intramolekulare
Aza‐Michael‐Addition
erzeugt.
anschließende
[1,5]‐sigmatrope
Kohlenstoffmigration
bildet
entsprechenden
Tetrahydrochinolin‐4‐one
in
61–98
%
Ausbeute
mit
exzellenten
Diastereoselektivitäten
von
d.r.
>99
:
1.
European Journal of Organic Chemistry,
Год журнала:
2023,
Номер
26(26)
Опубликована: Июнь 14, 2023
Abstract
The
1,4‐conjugated
addition
of
nitrogen
centered
nucleophiles
to
electron‐deficient
alkenes,
historically
called
the
aza‐Michael
addition,
is
one
most
significant
and
widely
used
reactions
in
modern
synthetic
organic
chemistry.
In
last
decade,
great
progress
has
been
made
this
field
namely
development
various
catalytic
systems.
Fundamental
advances
involve
use
transition
metal
catalysts,
organocatalysts,
enzymes,
ionic
liquids,
Brønsted
Lewis
acids
bases.
This
Review
aims
critically
analyze
results
research
into
aliphatic
aromatic
amines
with
Michael
acceptors.
Advanced Synthesis & Catalysis,
Год журнала:
2022,
Номер
364(10), С. 1622 - 1642
Опубликована: Апрель 8, 2022
Abstract
Aza‐Michael
addition
is
known
to
be
one
of
the
most
exploited
reactions
in
organic
chemistry.
Taking
into
account
fact
that
each
seventh
reaction
pharmaceutical
industry
involves
formation
at
least
C−N
bond,
it
not
surprising
this
especially
valuable
for
synthesis
bioactive
compounds
and
drugs.
Traditionally,
only
push‐pull
alkenes
are
regarded
as
starting
material
reaction.
The
participation
pull‐pull
Michael
acceptors
much
less
studied.
presence
two
vicinal
electron‐withdrawing
groups
makes
them
highly
reactive
nucleophilic
with
nitrogen‐centered
nucleophiles.
This
feature
allows
excellent
building
blocks
molecules
polyfunctional
materials.
review
considers
important
sometimes
unexpected
results
obtained
over
last
decades
on
conjugate
nitrogen
nucleophiles
bearing
various
acceptor
moieties
(alkoxycarbonyl‐,
carbonyl‐,
formyl‐,
cyano‐,
trifluoromethyl‐
or
nitro
group)
combinations.
magnified
image
Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
365(12), С. 1908 - 1925
Опубликована: Май 15, 2023
Abstract
The
1,4‐conjugated
addition
of
nitrogen
centered
nucleophiles
to
electron‐deficient
alkenes
is
one
the
most
significant
and
widely
used
reactions
in
modern
synthetic
organic
chemistry.
To
date,
various
protocols
for
aza‐Michael
reaction
have
been
developed.
However,
these
reports
mainly
focus
on
use
strong
Michael
donors.
In
recent
years,
conjugate
weak
acceptors
gained
increasing
popularity.
Impressive
progress
this
area
has
achieved
by
more
efficient
catalyst
systems.
This
review
aims
provide
a
critical
analysis
results
obtained
(azoles,
pyrroles,
indoles,
carbamates,
purines,
amides,
hydrazides,
uraciles
etc
)
with
which
were
reported
over
past
twelve
years.
Organic Letters,
Год журнала:
2023,
Номер
25(38), С. 6993 - 6998
Опубликована: Сен. 20, 2023
A
unified
strategy
has
been
developed
to
utilize
hydrazine
hydrate
in
asymmetric
organic
synthesis
by
overcoming
the
rapid
background
reaction
with
dienone.
The
H-bond
donor
ability
of
cinchona-alkaloid-derived
squaramide
catalyst
unlocks
this
previously
deemed
infeasibility.
dissymmetric
addition
symmetrical
dienones
tolerates
various
substitutions,
resulting
formation
optically
pure
fused
pyrazoline
derivatives
under
mild
conditions.
Furthermore,
scalability
methodology
and
a
successful
demonstration
postsynthetic
transformations
have
accomplished.
Organic Letters,
Год журнала:
2024,
Номер
26(8), С. 1533 - 1538
Опубликована: Фев. 16, 2024
A
highly
enantioselective
organocatalytic
aza-Michael
addition
of
4-nitro-pyrazole
to
ethyl
(E)-2,2-difluoro-5-oxopent-3-enoate
has
been
developed.
This
reaction
enabled
a
concise,
four-step,
stereoselective
synthesis
functionalized
3,3-difluoro-4-pyrazolo-piperidine
GSK3901383A,
key
intermediate
for
the
leucine-rich
repeat
kinase
2
inhibitor
API.
Computational
analysis
provided
insight
into
steric
requirements
catalytic
system,
enabling
rational
selection
selective
catalyst.
Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
365(17), С. 2789 - 2817
Опубликована: Июль 6, 2023
Abstract
Quaternary
stereogenic
centers
are
of
great
importance
because
their
prevalence
in
a
series
bioactive
natural
products
and
pharmaceuticals.
Although
the
catalytic
asymmetric
construction
these
highly
congested
poses
formidable
challenge,
this
field
has
been
extensively
explored
past
few
decades,
several
elegant
strategies,
such
as
conjugate
addition
to
β,β‐disubstituted
nitroalkenes,
have
developed.
The
resultant
β‐nitro
quaternary
stereocenters
can
be
conveniently
transformed
into
corresponding
β‐amino
commonly
found
compounds.
This
review
summarizes
recent
advances
all‐carbon
or
hetero‐carbon
via
metal‐catalyzed
organocatalyzed
focusing
on
scope,
applications,
mechanisms
reactions.
RSC Advances,
Год журнала:
2024,
Номер
14(21), С. 14835 - 14846
Опубликована: Янв. 1, 2024
In
this
work,
we
have
described
the
use
of
α-bromonitrostyrenes
in
synthesis
a
wide
variety
carbocyclic
and
heterocyclic
compounds
under
organocatalysis,
metal
catalysis,
base-catalysis
systems
as
well
catalyst-free
reactions.
Organic Letters,
Год журнала:
2022,
Номер
24(8), С. 1647 - 1651
Опубликована: Фев. 17, 2022
The
highly
enantioselective
aza-Michael
reaction
of
tert-butyl
β-naphthylmethoxycarbamate
to
cyclic
enones
has
been
accomplished
by
using
a
new
cinchona
alkaloid
derived
C(9)-urea
ammonium
catalyst
under
phase-transfer
catalysis
conditions
with
up
98%
ee
at
0
°C.
resulting
adducts
can
be
converted
versatile
intermediates
selective
deprotection
and
the
1,3-aminoalcohols
diastereoselective
reduction
32:1,
which
have
widely
used
as
important
pharmacophores
in
pharmaceutical
development.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(31)
Опубликована: Май 10, 2022
The
stereospecific
sigmatropic
[1,5]
carbon
shift
of
C3
ammonium
enolates
is
discovered.
According
to
mechanistic,
kinetic
and
computational
experiments,
this
new
rearrangement
proceeds
via
the
catalytic
generation
a
transient
enolate
by
intramolecular
aza-Michael
addition.
This
intermediate
rapidly
undergoes
migration
furnish
respective
tetrahydroquinoline-4-ones
with
excellent
diastereoselectivities
d.r.
>99
:
1
in
61-98
%
yield.