The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(8), С. 5363 - 5370
Опубликована: Апрель 9, 2024
The
density
functional
theory
(DFT)
was
employed
to
theoretically
investigate
the
reaction
mechanism
of
alcohol
deoxygenation/trifluoromethylation.
substrate
(R1)
forms
a
complex
(INT3)
by
binding
with
benzoxazole
salts
(NHCs).
Under
influence
photocatalyst
([IrIII]*)
and
quinuclidine,
C–H
bond
in
INT3
is
activated
through
either
electron
transfer-proton
transfer
(ETPT)
or
hydrogen
atom
(HAT)
mechanisms,
resulting
cleavage
C–O
bonds
generation
deoxyalkyl
radicals.
distribution
high-valent
low-valent
states
catalytic
cycle
[Ir]-complexes
governed
redox
potential
mechanism.
Investigation
conducted
on
source
reagents
HAT
process
under
both
optimal
nonoptimal
conditions.
results
demonstrate
distinct
reactivity
among
various
radicals
involved
Cu-mediated
radical
capture
process.
Further
investigations
into
activation
modes,
cycling
facilitated
[Ir]-complexes,
understanding
role
played
[Cu]-complexes
this
system
provide
valuable
theoretical
foundation
for
comprehending
enhancing
Ir/Cu
bimetallic
cooperative
catalysis
deoxygenation/trifluoromethylation
reactions.
This
provides
anticipated
support
future
designs
more
efficient
rational
deoxygenation
The Journal of Organic Chemistry,
Год журнала:
2022,
Номер
87(11), С. 7487 - 7493
Опубликована: Май 24, 2022
Ti-mediated
homolytic
C-O
bond
cleavage
was
useful
for
cascade
radical-ionic
reactions.
Benzyl
alcohols
treated
with
TiCl4(col)
(col
=
2,4,6-collidine)
and
Mn
powder
generated
the
corresponding
benzyl
radicals;
in
addition,
their
reaction
2-carboxyallyl
acetates
subsequent
elimination
of
acetoxy
group
yielded
α,β-unsaturated
carbonyl
compounds
exclusive
(E)-stereoselectivity.
The
simplicity
procedure
its
wide
substrate
scope
represent
a
solution
to
drawbacks
associated
Cell Reports Physical Science,
Год журнала:
2023,
Номер
4(7), С. 101474 - 101474
Опубликована: Июнь 27, 2023
The
direct
use
of
alcohols
as
coupling
partners
via
homolytic
C–OH
bond
cleavage
remains
a
formidable
challenge
but
holds
great
opportunities
to
achieve
useful
transformations.
In
this
context,
the
free
precursors
carbon
radicals
in
nickel-catalyzed
asymmetric
dicarbofunctionalization
tethered
olefins
is
highly
desirable.
Reported
herein
an
reductive
aryl-benzylation
alkenes
using
benzyl
mediated
by
nickel-titanium
bimetallic
system.
reaction
affords
corresponding
chiral
benzene-fused
cyclic
compounds
including
oxindoles,
dihydrobenzofurans,
tetralins,
indane,
and
isochroman
bearing
all-carbon
quaternary
stereocenter
with
up
99%
enantiomeric
excess.
practical
utilities
protocol
are
demonstrated
late-stage
modification
some
scaffolds
pharmaceuticals
natural
products.
This
study
shows
that
key
success
merging
titanium-mediated
homolysis
alcoholic
C–O
bonds
olefin
difunctionalization.
Organic Letters,
Год журнала:
2024,
Номер
26(11), С. 2315 - 2320
Опубликована: Март 8, 2024
Ether
C–O
bonds
are
typical
constituents
of
organic
molecules
that
seldom
regarded
as
reactive
functional
groups
except
when
highly
strained.
With
the
assistance
appropriate
directing
groups,
low-valent
titanium
was
found
to
homolytically
cleave
non-strained
bonds.
In
particular,
a
newly
designed
catechol
monoether
group
rendered
route
toward
activation
non-benzylic
C(sp3)–O
This
method
has
been
applied
conventional
radical
addition
reactions
alkenes.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(8), С. 5363 - 5370
Опубликована: Апрель 9, 2024
The
density
functional
theory
(DFT)
was
employed
to
theoretically
investigate
the
reaction
mechanism
of
alcohol
deoxygenation/trifluoromethylation.
substrate
(R1)
forms
a
complex
(INT3)
by
binding
with
benzoxazole
salts
(NHCs).
Under
influence
photocatalyst
([IrIII]*)
and
quinuclidine,
C–H
bond
in
INT3
is
activated
through
either
electron
transfer-proton
transfer
(ETPT)
or
hydrogen
atom
(HAT)
mechanisms,
resulting
cleavage
C–O
bonds
generation
deoxyalkyl
radicals.
distribution
high-valent
low-valent
states
catalytic
cycle
[Ir]-complexes
governed
redox
potential
mechanism.
Investigation
conducted
on
source
reagents
HAT
process
under
both
optimal
nonoptimal
conditions.
results
demonstrate
distinct
reactivity
among
various
radicals
involved
Cu-mediated
radical
capture
process.
Further
investigations
into
activation
modes,
cycling
facilitated
[Ir]-complexes,
understanding
role
played
[Cu]-complexes
this
system
provide
valuable
theoretical
foundation
for
comprehending
enhancing
Ir/Cu
bimetallic
cooperative
catalysis
deoxygenation/trifluoromethylation
reactions.
This
provides
anticipated
support
future
designs
more
efficient
rational
deoxygenation
