Angewandte Chemie,
Год журнала:
2024,
Номер
136(34)
Опубликована: Июнь 7, 2024
Abstract
A
photocatalyzed
formal
(3+2)
cycloaddition
has
been
developed
to
construct
original
polysubstituted
α‐SCF
3
cyclopentanones
in
a
regio‐
and
diastereoselective
manner.
This
building
block
approach
leverages
trifluoromethylthio
alkynes
branched/linear
aldehydes,
as
readily
available
reaction
partners,
consecutive
hydrogen
atom
transfers
C−C
bond
formations.
Difluoromethylthio
are
also
compatible
substrates.
Furthermore,
the
potential
for
telescoped
starting
from
alcohols
instead
of
aldehydes
was
demonstrated,
well
process
automatization
scale‐up
under
continuous
microflow
conditions.
prompted
density
functional
theory
(DFT)
calculations
support
radical‐mediated
cascade
process.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(7)
Опубликована: Янв. 2, 2024
Chromium-catalyzed
enantioselective
Nozaki-Hiyama-Kishi
(NHK)
reaction
represents
one
of
the
most
powerful
approaches
for
formation
chiral
carbon-heteroatom
bond.
However,
construction
sterically
encumbered
tetrasubstituted
stereocenter
through
NHK
still
posts
a
significant
challenge.
Herein,
we
disclose
cobalt-catalyzed
aza-NHK
ketimine
with
alkenyl
halide
to
provide
convenient
synthetic
approach
manufacture
enantioenriched
α-vinylic
amino
acid.
This
protocol
exhibits
excellent
functional
group
tolerance
99
%
ee
in
cases.
Additionally,
this
asymmetric
reductive
method
is
also
applicable
aldimine
access
trisubstituted
stereogenic
centers.
Organic & Biomolecular Chemistry,
Год журнала:
2024,
Номер
22(19), С. 3799 - 3842
Опубликована: Янв. 1, 2024
Tetrabutylammonium
decatungstate
(TBADT)
has
recently
emerged
as
an
intriguing
photocatalyst
under
visible-light
or
near-visible-light
irradiation
in
a
wide
range
of
organic
reactions
that
were
previously
not
conceivable.
Given
its
ability
to
absorb
visible
light
and
excellent
effectiveness
activating
unactivated
chemical
bonds,
it
is
promising
addition
traditional
photocatalysts.
This
review
covers
some
the
contemporary
developments
photocatalysis
enabled
by
TBADT
catalyst
2023,
with
contents
organized
reaction
type.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(25)
Опубликована: Янв. 22, 2024
β-Tertiary
amino
acid
derivatives
constitute
one
of
the
most
frequently
occurring
units
in
natural
products
and
bioactive
molecules.
However,
efficient
asymmetric
synthesis
this
motif
still
remains
a
significant
challenge.
Herein,
we
disclose
cobalt-catalyzed
enantioselective
reductive
addition
reaction
ketimine
using
α-chloro
carbonyl
compound
as
radical
precursor,
providing
expedient
access
to
diverse
array
enantioenriched
β-quaternary
analogues.
This
protocol
exhibits
outstanding
enantioselectivity
broad
substrate
scope
with
excellent
functional
group
tolerance.
Preliminary
mechanism
studies
rule
out
possibility
Reformatsky-type
confirm
involvement
species
stereoselective
process.
The
synthetic
utility
has
been
demonstrated
through
rapid
assembly
iterative
oligopeptide,
showcasing
its
versatile
platform
for
late-stage
modification
drug
candidates.
Chemistry - A European Journal,
Год журнала:
2024,
Номер
30(62)
Опубликована: Авг. 10, 2024
The
difunctionalization
of
alkenes
represents
a
powerful
tool
to
incorporate
two
functional
groups
into
the
alkene
bones
for
increasing
molecular
complexity
and
has
been
widely
utilizations
in
chemical
synthesis.
Upon
catalysis
green,
sustainable,
mild
photo-/electrochemistry
technologies,
much
attentions
have
attracted
development
new
tactics
transformations
important
alkane
feedstocks
driven
by
C-H
radical
functionalization.
Herein,
we
summarize
recent
advances
photo-/electrocatalytic
enabled
We
detailedly
discuss
substrate
scope
mechanisms
reactions
selecting
impressive
synthetic
examples,
which
are
divided
four
sections
based
on
final
terminated
step,
including
oxidative
radical-polar
crossover
coupling,
reductive
radical-radical
transition-metal-catalyzed
coupling.
Organic Letters,
Год журнала:
2024,
Номер
26(11), С. 2297 - 2302
Опубликована: Март 11, 2024
We
report
a
deoxygenative
amidation
reaction
of
alcohols
with
carbamoyl
chlorides
to
afford
amides
through
nickel–photoredox
dual
catalysis.
Good
excellent
yields
can
be
obtained
even
for
diverse
complex
sugar
and
steroid
derivatives.
The
is
scalable,
the
synthetic
utility
was
demonstrated
by
homologation
deliver
several
important
γ-amino
synthetically
challenging
bioactive
compound
intermediate.
ACS Catalysis,
Год журнала:
2024,
Номер
14(16), С. 12181 - 12191
Опубликована: Июль 30, 2024
The
advancement
of
sophisticated
synthetic
methodologies
that
streamline
reaction
processes
while
enhancing
molecular
complexity
is
a
perpetual
necessity
in
the
realm
chemistry.
Catalytic
one-pot
cascade
play
crucial
role
efficient
construction
intricate
molecules
with
exceptional
chemoselectivity.
Herein,
we
present
approach
for
synthesis
polycyclic
fused
δ-lactams
via
sequential
phosgenation,
Pd/NBE-catalyzed
ortho-carbamoylation/ipso-Heck-type
cyclization,
and
C–H
activation
from
readily
available
aryl
halides,
amines,
triphosgenes.
This
stands
out
as
first
example
situ
carbamoyl
chloride
formation
amine
precursors,
presenting
an
alternative
to
existing
transformations
involving
chlorides.
practical
significance
these
showcased
by
81
rapid
economically
favorable
manner,
without
need
intermediate
purification.
Moreover,
were
scalable
compatible
various
natural
products
pharmaceuticals,
further
underscoring
effectiveness
this
strategy.
relatively
rigid
coplanar
structure
displayed
our
synthesized
exhibits
distinct
room-temperature
phosphorescence
characteristics,
which
have
been
utilized
anticounterfeiting
high-security-level
data
encryption.
Chemistry - A European Journal,
Год журнала:
2024,
Номер
30(67)
Опубликована: Авг. 13, 2024
Abstract
Difunctionalizations
of
alkenes
represent
one
the
most
straightforward
protocols
to
build
molecular
complexity
due
simultaneous
construction
two
vicinal
bonds
cross
π‐bond
alkenes.
It
is
extremely
attractive
yet
challenging
control
stereochemistry
outcome
this
event.
Over
past
years,
visible‐light
and
Ni‐catalyzed
asymmetric
difunctionalizations
provide
an
environmental
benign
promising
solution
for
saturated
carbon
centers
with
regio‐
enantioselectivity.
In
Concept,
initiative
progress
enantioselective
enabled
by
nickel
catalysis
has
been
summarized.
Moreover,
further
efforts
directions
development
mediated
discussed.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 12, 2024
Enantioenriched
unnatural
amino
acids
represent
a
prevalent
motif
in
organic
chemistry,
with
profound
applications
biochemistry,
medicinal
and
materials
science.
Herein,
we
report
cobalt-catalyzed
aza-Barbier
reaction
of
dehydroglycines
unactivated
alkyl
halides
to
afford
α-amino
esters
high
enantioselectivity.
This
catalytic
reductive
alkylative
addition
protocol
circumvents
the
use
moisture-,
air-sensitive
organometallic
reagents,
stoichiometric
chiral
auxiliaries,
enabling
conversion
variety
primary,
secondary,
even
tertiary
α-alkyl-amino
under
mild
conditions,
thus
leading
broad
functional
group
tolerance.
The
expedient
access
biologically
active
motifs
demonstrates
practicality
this
by
reducing
number
synthetic
steps
enhancing
efficiency.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 3, 2024
The
Barbier
reaction
is
a
reductive-type
addition
of
an
aldehyde
or
ketone
with
organic
electrophile
in
the
presence
terminal
metal
reductant,
providing
straightforward
and
efficient
method
for
carbon-carbon
bond
formation.
This
possesses
advantage
circumventing
preparation
moisture-
air-sensitive
organometallic
reagents.
However,
catalytic
ketones
to
construct
tetrasubstituted
stereogenic
centers
largely
underdeveloped,
despite
its
great
potential
accessing
synthetically
challenging
chiral
tertiary
alcohol.
Particularly,
leveraging
unactivated
alkyl
electrophiles
as
coupling
components
still
rarely
exploited.
Herein,
we
disclose
photoredox-assisted
cobalt-catalyzed
asymmetric
alkylative
Barbier-type
address
aforementioned
challenges,
thereby
allowing
construction
highly
congested
carbon
centers.
fragments
could
be
either
readily
accessible
halides
redox-active
esters
generated
through
decarboxylative
pathway.
Both
types
include
primary,
secondary,
ones,
thus
affording
diverse
enantioenriched
alcohols
broad
substrate
scope.
enantioselective
protocol
applied
expedient
synthesis
core
structure
