Molecules,
Journal Year:
2023,
Volume and Issue:
28(2), P. 787 - 787
Published: Jan. 12, 2023
In
recent
years,
the
importance
of
“environmentally
friendly
manufacturing”
has
been
increasing
toward
establishment
a
resource-recycling
society.
organic
synthesis,
as
well,
it
is
becoming
increasingly
important
to
develop
new
synthetic
strategies
with
resource
conservation
and
recycling
elemental
resources
in
mind,
rather
than
just
only
synthesis.
Many
studies
on
construction
frameworks
functional
molecules
using
ionic
reactions
transition-metal-catalyzed
have
reported,
but
most
them
focused
formation
carbon–carbon
bonds.
However,
essential
introduce
appropriate
groups
at
positions
order
for
express
their
functions,
furthermore,
highly
selective
preparation
multiple
considered
creation
molecules.
this
review,
we
focus
radical
high
group
selectivity
overview
progress
practical
methods
simultaneous
introduction
propose
future
that
emphasize
environmental
friendliness.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(25)
Published: April 11, 2024
Abstract
While
polyborylated
alkenes
are
being
recognized
for
their
elevated
status
as
highly
valuable
reagents
in
modern
organic
synthesis,
allowing
efficient
access
to
a
diverse
array
of
transformations,
including
the
formation
C−C
and
C‐heteroatom
bonds,
potential
energy‐transfer
reactive
groups
has
remained
unexplored.
Yet,
this
holds
key
generating
elusive
biradical
species,
which
can
be
captured
by
olefins,
thereby
leading
construction
new
highly‐borylated
scaffolds.
Herein,
we
report
designed
strategy
photosensitized
[2+2]‐cycloadditions
poly‐borylated
with
various
olefins
enabling
regioselective
synthesis
cyclobutane
motifs,
1,1‐di‐,
1,1,2‐tri‐,
1,1,2,2‐tetra‐borylated
cyclobutanes.
In
fact,
these
compounds
belong
family
that
presently
lacks
synthetic
pathways.
Interestingly,
when
α‐methylstyrene
was
used,
reaction
involves
an
interesting
1,5‐hydrogen
atom
transfer
(HAT).
Mechanistic
deuterium‐labeling
studies
have
provided
insight
into
outcome
process.
addition,
cyclobutanes
then
demonstrated
useful
selective
oxidation
processes
resulting
cyclobutanones
γ‐lactones.
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(4), P. 1100 - 1104
Published: Jan. 26, 2022
Radical
1,3-carboheteroarylation
and
1,3-hydroalkylation
of
allylboronic
esters
comprising
a
1,2-boron
shift
is
reported.
Allylboronic
are
generally
used
in
synthesis
as
allylation
reagents,
where
the
boronic
ester
moiety
gets
lost.
In
introduced
cascades,
alkylboronic
obtained
with
boron
entity
remaining
product.
The
carboheteroarylation
conducted
without
metal
catalyst,
achieved
using
iron
catalysis.
Both
reactions
work
efficiently
under
mild
conditions.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(34)
Published: June 16, 2023
Abstract
Operationally
simple
strategies
to
assemble
boron
containing
organic
frameworks
are
highly
enabling
in
synthesis.
While
conventional
retrosynthetic
logic
has
engendered
many
platforms
focusing
on
the
direct
formation
of
C−B
bonds,
α‐boryl
radicals
have
recently
reemerged
as
versatile
open‐shell
alternatives
access
organoborons
via
adjacent
C−C
bond
formation.
Direct
light‐enabled
α‐activation
is
currently
contingent
photo‐
or
transition
metal‐catalysis
activation
efficiently
generate
radical
species.
Here,
we
disclose
a
facile
α‐halo
boronic
esters
using
only
visible
light
and
Lewis
base
enable
homolytic
scission.
Intermolecular
addition
styrenes
facilitates
rapid
construction
E
‐allylic
esters.
The
simplicity
permits
strategic
merger
this
construct
with
selective
energy
transfer
catalysis
complimentary
stereodivergent
synthesis
Z
Organic & Biomolecular Chemistry,
Journal Year:
2020,
Volume and Issue:
18(44), P. 8939 - 8974
Published: Jan. 1, 2020
This
review
systematically
outlined
the
research
in
area
of
transition
metal
free
synthesis
alkyl
pinacol
boronates,
which
are
versatile
and
important
scaffolds
to
construct
diverse
organic
compounds.
Organic Letters,
Journal Year:
2021,
Volume and Issue:
23(21), P. 8246 - 8251
Published: Oct. 15, 2021
A
visible-light-triggered
radical
cascade
sulfonylation/aryl
migration/desulfonylation
and
C-S/Se
bond
formation
reaction
of
butenyl
benzothiazole
sulfone
with
thiosulfonates
or
selenosulfonates
is
developed.
This
study
affords
the
1,2,4-trifunctionalization
derivatives
under
mild
conditions.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(30)
Published: May 20, 2022
Abstract
A
novel
distal
radical
rearrangement
of
alkoxyphosphine
is
developed
for
the
first
time
and
applied
to
regioselective
fluoroalkylphosphorylation
unactivated
olefins.
By
employing
a
one‐pot
two‐step
reaction
(bis)homoallylic
alcohols,
organophosphine
chlorides,
fluoroalkyl
iodides
under
CFL
(compact
fluorescence
light)
irradiation,
series
fluoroalkylphosphorylated
alkyl
alcohols
are
easily
synthesized
by
regiospecific
installing
phosphonyl
onto
inner
carbon
terminal
olefins
further
iodination/hydroxylation.
Mechanism
studies
reveal
that
migration
undergoes
distinctive
cyclization/β‐scission
on
lone
electron
pair
phosphorus,
resulting
in
C−P
bond
formation
C−O
cleavage.
European Journal of Organic Chemistry,
Journal Year:
2022,
Volume and Issue:
2022(9)
Published: Jan. 12, 2022
Abstract
Organoboronates
are
synthetically
useful
and
highly
valuable
building
blocks
in
synthetic
medicinal
chemistry.
Two‐electron
reactions
allow
for
the
rapid
construction
of
organoboronates
via
nucleophilic
1,2‐boron
shift
boron
ate
complexes
or
MIDA‐mediated
1,2‐boryl
migration.
Radical
approaches
through
neutral
boronic
esters
have
been
demonstrated
to
be
feasible,
providing
complementary
methods
access
these
privileged
scaffolds.
In
this
Review,
recent
achievements
highlighted
future
opportunities
discussed,
with
an
emphasis
on
different
operative
modes
catalysis
reaction
pathways.
