ACS Catalysis,
Год журнала:
2022,
Номер
12(24), С. 15750 - 15757
Опубликована: Дек. 7, 2022
A
photochemical
synthesis
of
brominated
α,α-difluoro-γ-lactones
from
cinnamyl
alcohols
and
ethyl
bromodifluoroacetate
is
reported
via
one-pot
Giese
addition/lactonization/halogen-atom
transfer
(XAT)
processes.
This
transformation
provides
in
moderate
to
good
diastereoselectivities.
The
reaction
affords
a
rapid
increase
molecular
complexity
organofluorine
chemical
space.
Dispersion-corrected
density
functional
theory
(DFT)
calculations
experiments
support
lactonization-induced
radical
chain
mechanism
which
long-lived
intermediate
undergoes
diastereoselective
halogen-atom
restart
the
cycle.
Catalysts,
Год журнала:
2023,
Номер
13(7), С. 1056 - 1056
Опубликована: Июнь 30, 2023
Alkenes
and
their
related
analogs
are
ideal
starting
materials
for
organic
synthesis,
the
selective
difunctionalization
of
alkenes,
which
allows
simultaneous
introduction
two
neighboring
bonds,
has
gained
considerable
attention
in
recent
years.
In
particular,
photoredox-catalyzed
alkenes
also
been
accomplished,
regarded
as
an
increasingly
powerful
tool
synthesis
miscellaneous
interesting
molecular
scaffolds
environmentally
benign
economical
manner.
Several
exquisite
strategies
have
developed
to
facilitate
this
transformation,
such
photosensitizer-catalyzed
redox
reactions,
electron
donor-acceptor
(EDA)
complexes-mediated
photoreactions,
atom
transfer
radical
addition
(ATRA)
reactions.
This
literature
review
briefly
describes
most
key
progress
on
1,2-difunctionalization
various
structurally
diverse
including
1,2-dicarbofunctionalization,
1,2-carboheterofunctionalization,
1,2-diheterofunctionalization,
with
a
special
emphasis
mechanistic
details.
Chemical Communications,
Год журнала:
2023,
Номер
59(36), С. 5395 - 5398
Опубликована: Янв. 1, 2023
The
first
N-heterocyclic
carbene
organocatalytic
three-component
radical
relay
trifunctionalization
of
unactivated
alkenes
through
the
combination
remote
1,4-cyano
migration
and
alkylacylation
was
reported.
This
protocol
features
mild
reaction
conditions,
readily
available
materials,
excellent
regioselectivity,
capability
late-stage
functionalization.
ACS Catalysis,
Год журнала:
2023,
Номер
13(8), С. 5538 - 5543
Опубликована: Апрель 10, 2023
Herein,
we
disclose
a
Ni-catalyzed
1,1-difunctionalization
of
unactivated
terminal
alkenes
that
enables
the
incorporation
two
different
heteroatom
motifs
across
an
olefin
backbone,
thus
streamlining
access
to
α-aminoboronic
acid
derivatives
from
simple
precursors.
The
method
is
characterized
by
its
simplicity
and
generality
wide
number
coupling
counterparts.
Organometallics,
Год журнала:
2023,
Номер
42(14), С. 1746 - 1758
Опубликована: Март 15, 2023
The
conjugated
bis-guanidinate
(CBG)
supported
zinc
hydride,
[{LZnH}2;
L
=
{(ArHN)(ArN)-C═N–C═(NAr)(NHAr);
Ar
2,6-Et2-C6H3}]
(1)
(pre)-catalyzed
addition
of
E–H
(E
B,
C,
N,
and
O)
to
carbodiimides
is
presented.
Compound
1
catalyzed
the
reduction
with
pinacolborane
(HBpin),
terminal
alkynes,
primary
amines,
alcohols,
gave
a
series
N-boryl
formamidines,
propiolamidines,
guanidines,
isoureas
high
conversions.
All
these
reactions
display
good
tolerance
functional
groups.
These
proceeded
through
active
catalysts
intermediate
amidinate
(Zn-1,
Zn-1′,
Zn-3),
alkynyl
(Zn-2,
Zn-2′),
anilide
(Zn-4),
alkoxide
(Zn-5)
complexes,
which
have
been
characterized
by
multinuclear
NMR
HRMS
analyses.
Moreover,
compounds
Zn-2′,
Zn-4,
Zn-5
were
confirmed
single-crystal
X-ray
diffraction
studies.
Complete
catalytic
cycles
proposed
based
on
well-defined
intermediates
stoichiometric
experiments.
ACS Catalysis,
Год журнала:
2023,
Номер
13(7), С. 4421 - 4432
Опубликована: Март 17, 2023
Palladium-catalyzed
Wacker-type
reactions
occupy
a
central
place
in
organic
synthesis
with
important
implications
industry.
Pursuing
more
benign
protocols
by
replacing
palladium
first-row
transition
metals
allowed
the
identification
of
iron
as
privileged
one
last
few
years.
Although
anti-Markovnikov
selectivity
for
catalysts
is
well
developed,
Markovnikov-selective
still
afford
significant
quantities
alcohol
side-products,
and
reaction
intermediates
has
remained
elusive
so
far.
Herein,
we
present
an
catalyst
that
affords
Markovnikov
ketone
products
from
(hetero)aromatic
aliphatic
olefins
up
to
99%
under
ambient
conditions
190,000
turnover
numbers
frequencies
74
h–1
at
50
°C.
The
design
based
on
promiscuous
activity
encountered
family
cytochromes
P-450
enzymes,
it
enables
formation
iron-hydride
species
catalytically
relevant
conditions.
Substrate
scope
assessment
mechanistic
investigations
suggest
catalytic
cycle
competes
unprecedented
three
additional
cycles
(alcohol
formation,
hydrogenation,
reductive
homo-coupling)
depending
nature
olefin
The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
88(11), С. 7431 - 7447
Опубликована: Май 23, 2023
Three-component
selenofunctionalization
processes
of
olefins,
diselenides
and
sulfonamides,
water,
alcohols,
or
acids
utilizing
1-fluoropyridinium
triflate
(FP-OTf)
as
a
reaction
promoter
are
reported.
Under
the
optimal
conditions,
broad
range
vicinally
functionalized
selenide
derivatives
was
accessible
with
high
yields
excellent
functional
group
compatibilities.
Mechanistic
studies
revealed
that
FP-OTf
played
key
role
in
this
process.
Chinese Journal of Chemistry,
Год журнала:
2024,
Номер
42(9), С. 957 - 962
Опубликована: Янв. 18, 2024
Comprehensive
Summary
Multicomponent
alkene
1,2‐dicarbofunctionalizations
(DCFs)
have
emerged
as
a
powerful
strategy
to
rapidly
incorporate
both
two
carbon
subunits
across
one
C—C
double
bond
in
step
for
enhancing
molecular
complexity
and
diversity.
To
the
best
of
our
knowledge,
there
is
only
report
on
photoredox‐catalyzed
three‐component
DCFs
with
malonates
through
radical−radical
cross‐coupling,
while
radical‐polar
crossover
(RPC)‐type
were
still
rare.
Herein,
we
describe
redox‐neutral
RPC‐type
1,2‐dialkylation
styrenes
aldehydes
synergistic
Brønsted
base/photoredox
catalysis
system.
This
transition‐metal‐free
provides
an
efficient
clean
approach
broad
variety
δ‐hydroxy
esters
also
features
exceptionally
mild
conditions,
wide
compatibility
substrate
scope
functional
groups,
high
atomic
economy.
Moreover,
1,2‐alkylacylation
from
same
starting
materials
was
achieved
one‐pot
manner
such
coupling
subsequent
two‐electron
oxidation
process,
providing
set
δ‐keto
interest
pharmaceutical
research.
Organic Chemistry Frontiers,
Год журнала:
2022,
Номер
10(4), С. 866 - 871
Опубликована: Дек. 21, 2022
Synthesis
of
β-azido
alkylsulfones
through
a
photoredox-catalyzed
azido
sulfonylation
alkenes
with
DABCO·(SO
2
)
,
trimethylsilyl
azide
and
alkyl
thianthrenium
salts
is
developed.
Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
365(8), С. 1217 - 1223
Опубликована: Март 25, 2023
Abstract
An
oxidative
[3+2+1]
cyclization
of
enaminones
and
N
‐alkenyl‐2‐pyrrolidinone
is
described
for
the
synthesis
4‐alkylated
1,4‐dihydropyridines
(1,4‐DHPs).
By
using
terminal
olefin
as
C4
source
1,4‐DHP
skeleton,
this
synthetic
strategy
provides
a
series
1,4‐DHPs
through
1,1‐difunctionalization/cyclization
process.
In
protocol,
two
C(
sp
3
)−C(
2
)
bonds
)−N
bond
are
simultaneously
formed,
hydrogen
on
newly
formed
methyl
group
skeleton
confirmed
possible
mechanism
proposed.
magnified
image
Chemistry - A European Journal,
Год журнала:
2023,
Номер
29(43)
Опубликована: Май 23, 2023
Abstract
β
‐Amino
sulfones
are
commonly
found
structural
motifs
in
biologically
active
compounds.
Herein,
we
report
a
direct
photocatalyzed
amino‐sulfonylation
reaction
of
alkenes
for
the
efficicient
production
important
compounds
by
simple
hydrolysis
without
need
additional
oxidants
and
reductants.
In
this
transformation,
sulfonamides
worked
as
bifunctional
reagents,
simultaneously
generating
sulfonyl
radicals
N
‐centered
which
were
added
to
alkene
highly
atom‐economical
fashion
with
high
regioselectivity
diastereoselectivity.
This
approach
showed
functional
group
tolerance
compatibility,
facilitating
late‐stage
modification
some
bioactive
sulfonamide
molecules,
thereby
expanding
relevant
chemical
space.
Scaling
up
led
an
efficient
green
synthesis
apremilast,
one
best‐selling
pharmceuticals,
demonstrating
synthetic
utility
applied
method.
Moreover,
mechanistic
investigations
suggest
that
energy
transfer
(EnT)
process
was
operation.