Journal of Synthetic Organic Chemistry Japan,
Journal Year:
2023,
Volume and Issue:
81(10), P. 930 - 940
Published: Oct. 1, 2023
Photoinduced
reactions
have
received
much
attention
as
a
powerful
tool
to
access
kinetically
or
thermodynamically
prohibited
on
the
ground
state.
However,
these
been
developed
mainly
by
using
electro-negative
elements
such
C,
O,
N,
halogens
well
transition-metals.
On
other
hand,
we
revealed
nature
of
chemical
species
including
electro-positive
main-group
elements,
boron
(B),
silicon
(Si),
and
tin
(Sn),
excited
state,
developing
highly
reactive
selective
photoinduced
reactions.
For
diboron
(B-B)
reagents,
designed
anionic
photo-absorbing
borate
complex
enable
quadruple
borylation
reaction
terminal
alkynes
under
ultraviolet
irradiation.
stannyl
(Sn)
species,
that
illumination
anions
generates
triplet
diradicals,
which
showed
orthogonality
traditional
reagents
(cations,
anions,
radicals)
hydrostannylation
defluorostannylation
fluoroarenes.
silylborane
(Si-B)
dearomative
triple
elementalization
(carbo-silaboration)
quinolines
excitation
silyl-borate
complexes
without
need
for
any
catalyst.
Chemical Society Reviews,
Journal Year:
2024,
Volume and Issue:
53(12), P. 6600 - 6624
Published: Jan. 1, 2024
Dearomatization
has
emerged
as
a
powerful
tool
for
rapid
construction
of
3D
molecular
architectures
from
simple,
abundant,
and
planar
(hetero)arenes.
The
field
evolved
beyond
simple
dearomatization
driven
by
new
synthetic
technology
development.
With
the
renaissance
photocatalysis
expansion
activation
mode,
last
few
years
have
witnessed
impressive
developments
in
innovative
photochemical
methodologies,
enabling
skeletal
modifications
dearomatized
structures.
They
offer
truly
efficient
useful
tools
facile
highly
complex
structures,
which
are
viable
natural
product
synthesis
drug
discovery.
In
this
review,
we
aim
to
provide
mechanistically
insightful
overview
on
these
innovations
based
degree
alteration,
categorized
into
dearomative
functionalization
editing,
highlight
their
utilities.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(41)
Published: May 28, 2024
Dearomative
construction
of
multiply-fused
2D/3D
frameworks,
composed
aromatic
two-dimensional
(2D)
rings
and
saturated
three-dimensional
(3D)
rings,
from
readily
available
quinolines
has
greatly
contributed
to
drug
discovery.
However,
dearomative
cycloadditions
in
the
presence
photocatalysts
usually
afford
5,6,7,8-tetrahydroquinoline
(THQ)-based
polycycles,
access
1,2,3,4-THQ-based
structures
remains
limited.
Herein,
we
present
a
chemo-,
regio-,
diastereo-,
enantioselective
transformation
into
6-6-4-membered
without
any
catalyst,
through
combination
nucleophilic
addition
borate-mediated
[2+2]
photocycloaddition.
Detailed
mechanistic
studies
revealed
that
photoexcited
borate
complex,
generated
quinoline,
organolithium,
HB(pin),
accelerates
cycloaddition
suppresses
rearomatization
occurs
conventional
Based
on
our
analysis,
also
developed
further
photoinduced
affording
other
types
frameworks
isoquinoline
phenanthrene.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(49)
Published: Aug. 13, 2024
Abstract
The
1,2‐hydroxysilylation
of
alkenes
is
crucial
for
synthesizing
organosilicon
compounds
which
are
key
intermediates
in
material
science,
pharmaceuticals,
and
organic
synthesis.
development
strategies
employing
hydrogen
atom
transfer
pathways
currently
hindered
by
the
existence
various
competing
reactions.
Herein,
we
reported
a
novel
mechanochemical
strategy
triphasic
through
single‐electron‐transfer
pathway.
Our
approach
not
only
circumvents
competitive
reactions
to
enable
first‐ever
unactivated
but
also
pioneers
research
mechanic
force‐induced
under
ambient
conditions.
This
gentle
method
offers
excellent
compatibility
with
functional
groups,
operates
simple
solvent‐free
conditions,
ensures
rapid
reaction
time.
Preliminary
mechanistic
investigations
suggest
that
silylboronate
can
be
transformed
silicon
radical
highly
polarized
Li
2
TiO
3
particles
oxygen
ball‐milling
condition.
Advanced Synthesis & Catalysis,
Journal Year:
2023,
Volume and Issue:
365(10), P. 1591 - 1595
Published: May 3, 2023
Abstract
In
the
presence
of
Suginome
reagent
(PhMe
2
Si−Bpin),
a
large
panel
electron‐withdrawing
alkenes
was
successfully
converted
into
hydrosilylated
product
in
good
to
excellent
yields.
This
direct
electrochemical
hydrosilylation
does
not
require
exogenous
oxidants
and
catalysts.
Preliminary
mechanistic
study
supported
involvement
silyl
radical,
which
reacted
on
alkene.
magnified
image
Synlett,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 18, 2025
Abstract
Dearomative
functionalization
of
quinolines
expands
the
chemical
diversity
highly
functionalized
3D
frameworks,
such
as
1,2,3,4-
and
5,6,7,8-tetrahydroquinoline
derivatives,
which
are
important
pharmacophores,
with
minimal
synthetic
costs.
In
this
short
review,
we
cover
recent
reports
on
visible-light-induced
dearomative
an
emphasis
reaction
design/strategies
mechanistic
studies
provide
a
theoretical
basis
for
developing
further
syntheses
in
future.
1
Introduction
2
Functionalizations
through
Formation
Photoexcited
Quinolines
3
Reagents/Intermediates
4
Conclusion
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(11), P. 2180 - 2185
Published: March 11, 2024
We
have
developed
visible-light-induced
trans-hydroboration
of
diaryl
alkynes
via
direct
photoexcitation
in-situ-generated
diboron
complexes,
affording
previously
elusive
(E)-1,2-diaryl-vinylboronates
with
high
stereoselectivity.
Experimental,
spectroscopic,
and
theoretical
mechanistic
studies
revealed
that
the
triplet-state
borate
complex
facilitates
B–B
bond
cleavage
desired
C–B
formation.
This
methodology
does
not
require
any
catalyst
is
operationally
simple.
The
highly
borylated
1,2-diaryl
alkenes
[1-(2-borylphenyl)vinyl)boronates]
are
shown
to
be
useful
as
building
blocks.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
26(1), P. 247 - 251
Published: Dec. 19, 2023
Activation
of
bis(pinacolato)diboron
with
aromatic
lithium
amide
promotes
diboration
the
proximal
C–C
triple
bond,
leading
to
BN-embedded
compounds.
In
situ
treatment
initially
generated
spirocyclic
borate
intermediate
aqueous
acid
or
organometallic
reagents
enables
ligand
installation
on
endocyclic
boron
atom.
Communications Chemistry,
Journal Year:
2024,
Volume and Issue:
7(1)
Published: June 4, 2024
Abstract
Photolysis
is
an
attractive
method
in
organic
synthesis
to
produce
free
radicals
through
direct
bond
cleavage.
However,
this
method,
specific
irradiation
wavelengths
of
light
have
been
considered
indispensable
for
excitation
S
0
–S
n
or
–T
transitions.
Here
we
report
the
photoinduced
homolysis
electronegative
interelement
bonds
using
at
much
longer
than
theoretically
and
spectroscopically
predicted
This
long-wavelength
photolysis
proceeds
N–Cl,
N–F,
O–Cl
room
temperature
under
blue,
green,
red
LED
irradiation,
initiating
diverse
radical
reactions.
Through
experimental,
spectroscopic,
computational
studies,
propose
that
“hidden”
absorption
accessible
via
electronic
excitations
from
naturally
occurring
vibrationally
excited
ground
states
unbonded
due
electron-pair
repulsion
between
atoms.
Bulletin of the Chemical Society of Japan,
Journal Year:
2024,
Volume and Issue:
97(8)
Published: July 31, 2024
Abstract
Organic
photoreactions
have
received
much
attention
as
unique
tools
to
access
kinetically
and/or
thermodynamically
prohibited
products
in
the
ground
state.
These
been
based
mainly
on
using
elements
with
high
electronegativity
such
carbon
(C),
oxygen
(O),
nitrogen
(N),
halogens
(F,
Cl,
Br,
and
I)
well
transition
metals.
On
other
hand,
we
interested
characteristics
of
low
electronegativity,
boron
(B),
silicon
(Si),
tin
(Sn),
excited
state,
enabling
highly
reactive
selective
photoinduced
borylations,
silylations,
stannylations.
In
this
account,
highlight
our
latest
findings
concerning
diverse
organic
utilizing
B,
Si,
Sn
elements,
which
are
challenging
when
conventional
strategies.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(21), P. 15623 - 15629
Published: Oct. 9, 2024
We
have
developed
a
visible-light-induced
method
to
photolyze
digermanes
through
single-electron
oxidation
using
photocatalyst,
in
contrast
direct
excitation,
generate
germyl
radicals
and
achieve
the
hydro/deuteriogermylation
of
alkenes.
This
protocol
allows
previously
elusive
incorporation
small
trimethylgermyl
group
deuterium,
metabolically
stable
bioisosteres
tert-butyl
hydrogen,
respectively,
making
this
approach
attractive
not
only
organic
synthesis
but
also
medicinal
chemistry.
