Abstract
The
first
examples
of
tetrasubstituted
conjugated
bis‐guanidinate
(CBG)
supported
monomeric
and
thermally
stable
gallium
dihalides
[LGaX
2
],
(X=Cl
(
Ga−Cl
),
I
Ga−I
))
dihydride
Ga−H
)
[LGaH
]
(where
L={(ArHN)(ArN)−C=N−C=(NAr)(NHAr)};
Ar=2,6‐Et
−C
6
H
3
compounds
are
reported.
reaction
in
situ
generated
LLi
with
1.0
equiv.
GaX
(X=Cl,
I)
afforded
.
between
Li[HBEt
benzene
yielded
the
compound
All
reported
,
were
characterized
by
NMR,
HRMS,
single‐crystal
X‐ray
diffraction
studies.
was
probed
for
hydroboration
carbodiimides
(CDI),
isocyanates,
isothiocyanates
HBpin.
Compound
also
found
effective
catalytic
imines,
nitriles,
alkynes,
esters,
formates,
affording
corresponding
products
quantitative
yields.
Stoichiometric
reactions
a
CDI
performed
to
establish
cycle.
Chemical Society Reviews,
Год журнала:
2022,
Номер
51(16), С. 7206 - 7237
Опубликована: Янв. 1, 2022
This
review
covers
the
recent
progress
in
electro-/photo-catalytic
alkene-derived
radical
cation
chemistry
for
organic
synthesis,
including
synthetic
strategies,
plausible
mechanisms
and
further
research
outlook.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(20), С. 10991 - 10997
Опубликована: Май 15, 2023
Herein
we
disclose
a
strategy
to
promote
the
hydrocarboxylation
of
unactivated
alkenes
using
photochemical
activation
formate
salts.
We
illustrate
that
an
alternative
initiation
mechanism
circumvents
limitations
prior
approaches
and
enables
this
challenging
substrate
class.
Specifically,
found
accessing
requisite
thiyl
radical
initiator
without
exogenous
chromophore
eliminates
major
byproducts
have
plagued
attempts
exploit
similar
reactivity
for
alkene
substrates.
This
redox-neutral
method
is
technically
simple
execute
effective
across
broad
range
Feedstock
alkenes,
such
as
ethylene,
are
hydrocarboxylated
at
ambient
temperature
pressure.
A
series
cyclization
experiments
indicate
how
described
in
report
can
be
diverted
by
more
complex
processes.
Organic Letters,
Год журнала:
2024,
Номер
26(9), С. 1845 - 1850
Опубликована: Фев. 26, 2024
The
difunctionalization
of
alkenes
using
aryl
thianthrenium
salts
as
the
sources
has
been
reported
sporadically.
However,
four-component
on
basis
not
thus
far
and
still
remains
a
challenge.
Herein,
visible
light/copper
catalysis-enabled
reaction
salts,
DABCO·(SO
Organic Chemistry Frontiers,
Год журнала:
2022,
Номер
9(4), С. 917 - 922
Опубликована: Янв. 1, 2022
The
synthesis
of
β-azidosulfones
starting
from
alkenes,
cycloketone
oxime
esters,
trimethylsilyl
azide
and
a
sulfur
dioxide
surrogate
DABCO·(SO
2
)
under
iron
catalysis
is
developed.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(17)
Опубликована: Фев. 18, 2022
Abstract
We
herein
report
the
preparation
of
solid
and
salt‐stabilized
silylzinc
pivalates
from
corresponding
silyllithium
reagents
via
transmetalation
with
Zn(OPiv)
2
.
These
resulting
organosilylzinc
show
enhanced
air
moisture
stability
unique
reactivity
in
silylative
difunctionalization
alkenes.
Thus,
a
practical
chelation‐assisted
nickel‐catalyzed
regioselective
alkyl
benzylsilylation
alkenes
has
been
developed,
which
provides
an
easy
method
to
access
silanes
broad
substrate
scope
wide
functional
group
compatibility.
Kinetic
experiments
highlight
that
OPiv‐coordination
is
crucial
improve
pivalates.
Furthermore,
late‐stage
functionalizations
druglike
molecules
versatile
modifications
products
illustrate
synthetical
utility
this
protocol.
Organic Chemistry Frontiers,
Год журнала:
2023,
Номер
10(10), С. 2563 - 2580
Опубликована: Янв. 1, 2023
This
review
summarizes
the
synthesis
and
reactivity
of
N
-aminopyridinium
salts,
discusses
applications
in
organic
synthesis,
highlights
potential
for
these
reagents
to
enable
novel
synthetic
disconnections
innovations.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(15), С. 8299 - 8307
Опубликована: Апрель 6, 2023
Modular
strategies
to
rapidly
increase
molecular
complexity
have
proven
immensely
synthetically
valuable.
In
principle,
transformation
of
an
alkene
into
a
dielectrophile
presents
opportunity
deliver
two
unique
nucleophiles
across
alkene.
Unfortunately,
the
selectivity
profiles
known
dielectrophiles
largely
precluded
this
deceptively
simple
synthetic
approach.
Herein,
we
demonstrate
that
dicationic
adducts
generated
through
electrolysis
alkenes
and
thianthrene
possess
profile
relative
more
conventional
dielectrophiles.
Specifically,
these
species
undergo
single
perfectly
regioselective
substitution
reaction
with
phthalimide
salts.
This
observation
unlocks
appealing
new
platform
for
aminofunctionalization
reactions.
As
illustrative
example,
implement
reactivity
paradigm
address
longstanding
challenge:
diamination
distinct
nitrogen
nucleophiles.
Studies
mechanism
process
reveal
key
alkenyl
thianthrenium
salt
intermediate
controls
exquisite
regioselectivity
highlight
importance
proton
sources
in
controlling
sulfonium
electrophiles.
Chemical Science,
Год журнала:
2023,
Номер
14(22), С. 6045 - 6051
Опубликована: Янв. 1, 2023
A
photocatalytic
C-H
gem-difunctionalization
of
1,3-benzodioxoles
with
two
different
alkenes
for
the
synthesis
highly
functionalized
monofluorocyclohexenes
is
described.
Using
4CzIPN
as
photocatalyst,
direct
single
electron
oxidation
allows
their
defluorinative
coupling
α-trifluoromethyl
to
produce
gem-difluoroalkenes
in
a
redox-neutral
radical
polar
crossover
manifold.
The
bond
resultant
γ,γ-difluoroallylated
was
further
via
addition
electron-deficient
using
more
oxidizing
iridium
photocatalyst.
capture
situ
generated
carbanions
by
an
electrophilic
gem-difluoromethylene
carbon
and
consecutive
β-fluoride
elimination
afford
monofluorocyclohexenes.
synergistic
combination
multiple
termination
pathways
enables
rapid
incorporation
molecular
complexity
stitching
simple
readily
accessible
starting
materials
together.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(16)
Опубликована: Фев. 8, 2024
Oxidative
alkene
functionalization
reactions
are
a
fundamental
class
of
complexity-building
organic
transformations.
However,
the
majority
established
approaches
rely
on
electrophilic
reagents
that
limit
diversity
groups
can
be
installed.
Recent
advances
have
new
approach
instead
relies
transformation
alkenes
into
thianthrene-derived
cationic
electrophiles.
These
linchpin
intermediates
generated
selectively
and
undergo
diverse
array
mechanistically
distinct
with
abundant
nucleophiles.
Taken
together,
this
unlocks
suite
net
oxidative
transformations
been
elusive
using
conventional
strategies.
This
Minireview
describes
these
is
organized
around
three
synthons
formally
accessible
from
via
thianthrenation:
1)
alkenyl
cations;
2)
vicinal
dications;
3)
allyl
cations.
Throughout
Minireview,
we
illustrate
how
thianthrenium
salts
address
key
limitations
endemic
to
classic
alkene-derived
electrophiles
highlight
mechanistic
origins
distinctions
wherever
possible.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 17, 2025
1,2-Amino-difunctionalization
reactions
of
alkenes
allow
the
efficient
introduction
different
functional
groups
and
rapid
construction
valuable
functionalized
amines.
In
this
respect,
we
report
a
copper-catalyzed
1,2-amino-alkoxycarbonylation
unactivated
with
CO
alkylamine
precursors
in
presence
Lewis
acid
additive.
The
novel
protocol
allows
direct
access
to
β-amino
derivatives
from
easily
available
starting
materials.
presented
methods
feature
high
chemo-
regioselectivities,
good
group
tolerance,
substrate
scope
including
diverse
bioactive
compounds
drug-like
molecules.
Mechanistic
studies
indicate
that
additive
is
key
realizing
umpolung
addition
nucleophilic
aminyl
radicals
electron-rich
alkenes,
which
represents
an
elegant
activation
strategy
for
radicals.
