Journal of Synthetic Organic Chemistry Japan,
Год журнала:
2022,
Номер
80(1), С. 2 - 13
Опубликована: Янв. 1, 2022
Herein
we
report
our
recent
efforts
on
the
greener
catalytic
synthetic
methods
of
nitrogen-containing
compounds
using
N-unprotected
ketimines.
We
found
that
alkynylation
trifluoromethyl
ketimines
proceeded
in
presence
zinc
catalysts,
providing
products
good
yield
with
broad
functional
group
tolerance
and
unique
chemoselectivity.
Next,
extended
methodology
to
stereoselective
addition
reactions
a
direct
Mannich-type
reaction,
Friedel-Crafts-type
alkylation
decarboxylative
an
arylation
reaction
appropriate
metal
or
organocatalysts
give
α-tetrasubstituted
amines
high
stereoselectivity.
The
detailed
scope
some
mechanistic
insights
these
are
also
presented.
ACS Medicinal Chemistry Letters,
Год журнала:
2023,
Номер
14(4), С. 376 - 385
Опубликована: Март 8, 2023
The
generation
of
multiple
bonds
in
one
reaction
step
has
attracted
massive
interest
drug
discovery
and
development.
Multicomponent
reactions
(MCRs)
offer
the
advantage
combining
three
or
more
reagents
a
one-pot
fashion
to
effectively
yield
synthetic
product.
This
approach
significantly
accelerates
synthesis
relevant
compounds
for
biological
testing.
However,
there
is
perception
that
this
methodology
will
only
produce
simple
chemical
scaffolds
with
limited
use
medicinal
chemistry.
In
Microperspective,
we
want
highlight
value
MCRs
toward
complex
molecules
characterized
by
presence
quaternary
chiral
centers.
paper
cover
specific
examples
showing
impact
technology
clinical
recent
breakthroughs
expand
scope
topologically
rich
molecular
chemotypes.
Chemical Communications,
Год журнала:
2023,
Номер
59(54), С. 8343 - 8374
Опубликована: Янв. 1, 2023
Catalytic
enantioselective
synthesis
methodologies
have
been
actively
explored
and
developed
owing
to
the
significance
of
chiral
molecules
their
utilities.
In
particular,
unnatural
α-amino
acids
with
tetrasubstituted
stereogenic
carbon
centers
(α-tertiary
amino
acids;
ATAAs)
are
undoubtedly
among
most
valuable
compounds.
Asymmetric
addition
an
α-iminoester
or
α-iminoamide
is
widely
recognized
as
a
straightforward,
powerful,
atom-economical
strategy
for
accessing
optically
active
derivatives.
However,
this
type
chemistry,
which
relies
on
ketimine-type
electrophiles,
was
quite
limited
only
few
decades
ago
low
reactivities
difficulties
associated
enantiofacial
control.
This
feature
article
comprehensively
overviews
research
field
highlights
significant
progress
that
has
made.
it
focuses
catalyst
system
transition
state
key
parameters
such
reactions.
Catalysts,
Год журнала:
2022,
Номер
12(10), С. 1149 - 1149
Опубликована: Окт. 1, 2022
α-Aminonitriles,
which
have
anticancer,
antibacterial,
antiviral,
and
antifungal
properties,
played
an
important
role
in
pharmacology.
Furthermore,
they
can
also
be
used
to
synthesize
natural
unnatural
amino
acids.
The
main
bottleneck
the
commercialization
of
these
products
is
their
large-scale
production
with
controlled
chirality.
A
variety
methods
been
α-aminonitriles.
Among
other
reported
for
preparing
α-aminonitriles,
Strecker
reaction
considered
appropriate.
Recent
developments,
however,
enabled
α-cyanation
tertiary
secondary
amines
by
functionalizing
carbon–hydrogen
(C–H)
bond
as
attractive
alternative
procedure
preparation
α-aminonitriles
presence
oxidant
a
cyanide
source.
In
most
cases,
reactions
are
catalyzed
transition
metal
catalysts,
such
Fe,
Cu,
Rh,
V,
Au,
Ru,
Mo,
Pt,
Re,
Co,
or
photocatalysts.
As
alternative,
organocatalysts
produce
aminonitriles.
Although
there
numerous
reviews
on
no
published
specifically
organocatalyzed
synthesis
Organocatalysis
plays
significant
synthesizing
via
Strecker-type
cross
dehydrogenative
coupling
(CDC).
this
mini
review,
we
discuss
molecules.
review
new
aminonitriles
expected
provide
insight
into
development
industrial
catalysts.
Organic Letters,
Год журнала:
2024,
Номер
26(4), С. 900 - 905
Опубликована: Янв. 22, 2024
Asymmetric
cyanation
of
α-ketimino
esters
catalyzed
by
combined
systems
amino
acid/BINAP
derivative/Ru(II)
complexes
and
lithium
compounds
was
examined.
The
use
an
appropriate
combination
acid
BINAP
ligands
achieved
high
enantioselectivity
for
a
variety
α-alkynyl
(Val/XylBINAP/Ru),
α-alkenyl
(Val/TolBINAP/Ru),
α-aryl
imino
(Val/XylBINAP/Ru)
as
well
isatin-derived
cyclic
amide
(t-Leu/BINAP/Ru)
to
afford
the
α-cyano-α-amino
with
α-nitrogen-substituted
quaternary
chiral
center
up
98%
ee.
Organic Letters,
Год журнала:
2022,
Номер
24(43), С. 8088 - 8092
Опубликована: Окт. 24, 2022
The
first
enantioselective
hydrophosphonylation
of
ketimines
with
phosphine
oxides
was
developed.
reaction
unprotected
using
a
bis(imidazoline)-phosphoric
acid
catalyst
gave
chiral
α-quaternary
aminophosphorous
compounds
having
primary
amino
group
in
excellent
yields
and
enantioselectivities.
Based
on
experimental
results
DFT
calculation,
transition
states
were
proposed
to
explain
the
stereoselectivity
reaction.
A
practical
photoinduced
direct
N–O
cleavage
of
oxime
ethers
via
a
single
electron
transfer
(SET)
process
was
developed,
enabling
controlled
generation
N–H
imines
iminyl
radical
intermediates.
By
employing
this
strategy,
an
efficient
Strecker-type
reaction
established
to
construct
variety
primary
α-aminonitriles
using
TMSCN
as
cyanide
source.
This
protocol
showed
exceptional
tolerance
various
functional
groups,
delivering
the
corresponding
products
in
good
yields.
Mechanistic
investigations
indicate
involvement
radicals
and
radical/polar
crossover
sequence.
Symmetry,
Год журнала:
2022,
Номер
14(9), С. 1758 - 1758
Опубликована: Авг. 23, 2022
The
current
review
is
devoted
to
the
achievements
in
development
of
methods
for
catalytic
asymmetric
synthesis
phosphonates
containing
a
chiral
center
side
chain.
C-chiral
are
widely
represented
among
natural
compounds
with
various
biological
activities
as
insecticides,
herbicides,
antibiotics,
and
bioregulators.
Synthetic
representatives
this
class
have
found
practical
application
biologically
active
compounds.
summarizes
metal
complex
catalysis
organocatalysis
applied
such
reactions
phospha-aldol
reaction,
two-component
three-component
phospha-Mannich
phospha-Michael
well
hydrogenation
unsaturated
phosphine
oxides,
ketophosphonates,
iminophosphonates.
Methods
hydride
reduction
C=X
(X=O,
S,
NR)
also
discussed
detail.
presents
updated
literature
reports,
original
research
by
author.
Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
365(6), С. 871 - 876
Опубликована: Фев. 28, 2023
An
aerobic
Mn(III)-catalyzed
one-pot
three-component
synthesis
of
5-cyano-pyrazolo[1,5-a]pyrimidines
has
been
described.
The
synergistic
combination
Strecker
reaction
and
oxidatively-induced
6π-azacyclization
is
the
key
to
success
this
multicomponent
synthesis.
Differing
from
previous
reports
relied
on
toxic
cyanating
agents
or
multistep
synthesis,
mechanistically
distinct
protocol
serves
as
a
step-economic,
regioselective
functionally
tolerant
strategy
obtain
5-cyano-pyrazolo[1,5-a]pyrimidines.
As
service
our
authors
readers,
journal
provides
supporting
information
supplied
by
authors.
Such
materials
are
peer
reviewed
may
be
re-organized
for
online
delivery,
but
not
copy-edited
typeset.
Technical
support
issues
arising
(other
than
missing
files)
should
addressed
Please
note:
publisher
responsible
content
functionality
any
Any
queries
content)
directed
corresponding
author
article.
ACS Catalysis,
Год журнала:
2023,
Номер
13(5), С. 3158 - 3163
Опубликована: Фев. 17, 2023
We
report
an
organocatalyzed
direct
enantioselective
hydrophosphonylation
of
N-unsubstituted
ketimines
that
affords
N-unprotected
α-tetrasubstituted
α-aminophosphonates
without
protection/deprotection
steps.
The
reaction
is
suitable
for
isatin-derived
and
trifluoromethyl
ketimines,
affording
products
in
high
yields
with
excellent
enantioselectivity.
Applications
the
a
proposed
transition
state
model
are
also
described.
Organic Chemistry Frontiers,
Год журнала:
2021,
Номер
8(22), С. 6384 - 6389
Опубликована: Янв. 1, 2021
An
I
2
O
5
-mediated
multicomponent
reaction
that
allows
the
single-step
construction
of
cyano-functionalized
imidazo[1,5-
a
]pyridines
with
molecular
diversity
was
realized
for
first
time.