European Journal of Organic Chemistry,
Год журнала:
2022,
Номер
2022(43)
Опубликована: Окт. 14, 2022
Abstract
Allenyl
radicals
are
rarely
employed
as
intermediates
for
the
synthesis
of
allenes
probably
owe
to
lack
convenient
methods
their
generation
and
high
reactivity
short‐lived
allenyl
radicals.
However,
strategies
take
advantage
considered
a
significant
complement
reactions
which
couldn't
proceed
via
an
ionic
pathway.
As
result,
several
important
have
been
developed
in
past
decades.
Herein,
this
review
is
aimed
summarize
recent
advance
involving
by
highlighting
some
outstanding
challenges
confirming
potential
areas
improvement,
would
offer
inspiration
future
studies
Chemical Science,
Год журнала:
2022,
Номер
13(29), С. 8491 - 8506
Опубликована: Янв. 1, 2022
Allenes
are
valuable
organic
molecules
that
feature
unique
physical
and
chemical
properties.
They
not
only
often
found
in
natural
products,
but
also
act
as
versatile
building
blocks
for
the
access
of
complex
molecular
targets,
such
pharmaceuticals,
functional
materials.
Therefore,
many
remarkable
elegant
methodologies
have
been
established
synthesis
allenes.
Recently,
more
methods
radical
allenes
developed,
clearly
emphasizing
associated
great
synthetic
values.
In
this
perspective,
we
will
discuss
recent
important
advances
Chemical Communications,
Год журнала:
2022,
Номер
58(75), С. 10442 - 10468
Опубликована: Янв. 1, 2022
Fluorine
compounds
are
known
for
their
abundance
in
more
than
20%
of
pharmaceutical
and
agrochemical
products
mainly
due
to
the
enhanced
lipophilicity,
metabolic
stability
pharmacokinetic
properties
organofluorides.
Consequently,
last
decade
has
seen
enormous
growth
incorporation
a
trifluoromethyl
group
into
organic
motifs.
With
significance,
this
review
aims
provide
complete
picture
transition
metal-mediated
construction
C(sp3,
sp2,
sp)-CF3
bonds
via
C-H/X
bond
functionalization
or
addition
processes
both
aliphatic
aromatic
hydrocarbons.
Diversified
reagents
ranging
from
radical
electrophilic
nucleophilic
trifluoromethylating
agents
respective
mechanisms
have
been
further
deliberated
comprehensive
overview.
The
coverage
on
topic
is
expected
make
unique
beneficial
future
applications
enriching
community
towards
improvements
field
trifluoromethylation
reactions,
turn
improving
propensity
development
drugs.
The Journal of Organic Chemistry,
Год журнала:
2022,
Номер
87(8), С. 5229 - 5241
Опубликована: Март 29, 2022
An
N-heterocyclic
carbene
organocatalytic
1,4-difunctionalization
of
1,3-enynes
was
developed.
This
strategy
suitable
for
a
broad
spectrum
substrates
to
efficiently
synthesize
allenic
ketones
bearing
diverse
substituents.
Preliminary
mechanistic
studies
suggest
radical
reaction
pathway
this
acylalkylation
process.
Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
365(16), С. 2653 - 2675
Опубликована: Апрель 21, 2023
Abstract
Hypervalent
iodine
compounds
have
found
broad
application
in
modern
organic
chemistry
as
reagents
and
catalysts.
Cyclic
hypervalent
based
on
the
benziodoxole
heterocyclic
system
higher
stability
compared
to
their
acyclic
analogues,
which
makes
possible
preparation
safe
handling
of
with
special
ligands
such
azido,
cyano,
trifluoromethyl
groups.
Numerous
iodine‐substituted
derivatives
been
prepared
utilized
for
transfer
substituent
substrate.
Reactions
these
substrates
can
be
performed
under
metal‐free
conditions,
presence
transition
metal
catalysts,
or
using
photocatalysts
photoirradiation
conditions.
In
this
review,
we
focus
most
recent
synthetic
applications
cyclic
iodine(III)
following
ligands:
N
3
,
NHR,
CN,
CF
SCF
OR,
OAc,
ONO
2
C(=N
)CO
R.
The
review
covers
literature
published
mainly
last
5
years.
Organic Letters,
Год журнала:
2024,
Номер
26(2), С. 536 - 541
Опубликована: Янв. 5, 2024
In
the
presence
of
visible
light
irradiation,
organophoto/nickel
dual
catalysts,
and
mild
base
K2HPO4,
1,3-enynes
react
with
silanecarboxylic
acids
to
give
corresponding
α-silylallenes
high
selectivity.
this
uniquely
decarboxylative
hydrosilylation
1,3-enynes,
a
silyl
radical
process
is
involved
diverse
electron-rich
-poor
substrates
proceed
smoothly
in
moderate
excellent
yields.
This
transformation
particularly
synthetically
worthwhile
when
using
MeOD
as
solvent,
which
furnishes
new
access
α-silyldeuteroallenes.
Organic Letters,
Год журнала:
2021,
Номер
23(23), С. 9251 - 9255
Опубликована: Ноя. 17, 2021
The
radical
relay
coupling
reaction
recently
emerged
as
a
powerful
synthetic
strategy
for
producing
tetrasubstituted
allenes.
However,
bond-forming
processes
involving
the
allenyl
intermediate
are
mostly
limited
to
those
promoted
by
transition
metals.
In
this
report,
we
describe
that
ketyl
generated
from
single-electron
oxidation
of
Breslow
is
an
excellent
partner
radicals.
An
organocatalytic
1,4-alkylacylation
1,3-enynes
occurred
smoothly
in
presence
aldehyde,
precursor,
and
N-heterocyclic
carbene
catalyst.
This
transformation
showed
remarkable
tolerance
both
aromatic
aliphatic
aldehydes,
enyne
substitution,
diversified
precursors.
Molecules,
Год журнала:
2023,
Номер
28(7), С. 3027 - 3027
Опубликована: Март 28, 2023
Radical
transformations
are
powerful
in
organic
synthesis
for
the
construction
of
molecular
scaffolds
and
introduction
functional
groups.
In
radical
difunctionalization
reactions,
radicals
first
functionalized
intermediates
can
be
relocated
through
resonance,
hydrogen
atom
or
group
transfer,
ring
opening.
The
resulting
undertake
following
paths
second
functionalization:
(1)
couple
with
other
groups,
(2)
oxidize
to
cations
then
react
nucleophiles,
(3)
reduce
anions
electrophiles,
(4)
metal-complexes.
rearrangements
provide
opportunity
1,3-,
1,4-,
1,5-,
1,6-,
1,7-difunctionalization
products.
Multiple
ways
initiate
reaction
coupling
intermediate
make
reactions
good
at
remote
positions.
These
offer
advantages
synthetic
efficiency,
operation
simplicity,
product
diversity.
ACS Catalysis,
Год журнала:
2023,
Номер
13(3), С. 2142 - 2148
Опубликована: Янв. 25, 2023
Allenol
has
been
identified
as
a
versatile
building
block
for
organic
synthesis,
and
numerous
efforts
have
made
to
synthesize
apply
allenol.
However,
limited
obtain
trifluoromethyl-substituted
Here,
by
using
readily
available
1,3-enyne
the
starting
material,
copper-catalyzed
trifluoromethylbenzoxylation
process
was
developed
efficient
synthesis
of
allenols
Togni-II
reagent
reaction
partner.
Triple
roles
reagent,
including
source
trifluoromethyl
group,
hydroxyl
oxidant,
were
elucidated
in
this
transformation.
Moreover,
late-stage
diversification
performed,
which
revealed
application
potential
preparation
various
compounds.
Organic Letters,
Год журнала:
2023,
Номер
25(14), С. 2509 - 2514
Опубликована: Апрель 3, 2023
The
Cu(I)-catalyzed
annulation-halotrifluoromethylation
and
cyanotrifluoromethylation
of
enynones
have
been
established,
enabling
multibond
formations
the
synthesis
quaternary
carbon-centered
1-indanones
in
moderate
to
good
chemical
yields.
reaction
with
Togni's
reagent
chloro-
or
bromotrimethylsilane
afforded
halo-
CF3-containing
1-indenones.
However,
addition
K3PO4
as
a
base
into
catalytic
system
led
forming
cyano-anchored
(Z)-1-indanones
major
stereoisomeric
products.
This
strategy
exhibits
remarkable
compatibility
wide
range
enynones.
Organic Letters,
Год журнала:
2024,
Номер
26(9), С. 1834 - 1839
Опубликована: Фев. 22, 2024
Efficient
access
to
multiple
functionalized
allenes
via
a
three
component
1,4-alkylcyanation
of
enynes
with
cyclic
alcohol
derivatives
in
the
presence
trimethylsilyl
cyanide
(TMSCN)
under
copper/photoredox
dual
catalysis
has
been
developed.
Both
easily
transformable
aldehyde
and
cyano
groups
were
introduced
tetra-substituted
through
light-induced
C–C
bond
cleavage
butanol
pentanol
derivatives.
The
reactions
proceeded
smoothly
mild
conditions
broad
functional
tolerance.
