Chinese Journal of Chemistry,
Год журнала:
2024,
Номер
42(19), С. 2329 - 2334
Опубликована: Май 22, 2024
Comprehensive
Summary
A
visible
light
photocatalytic
[3+2]
cycloaddition
of
alkynes
with
readily
accessible
organic
iodides
as
the
C3
synthon
is
developed
herein.
By
merging
halogen
atom
transfer
(XAT)
and
hydrogen
(HAT),
alkyl/aryl
serve
a
formal
diradical
precursor
add
across
C‐C
triple
bonds
to
deliver
number
functionalized
cyclopentanes
in
moderate
high
yields
exceptional
regio‐
diastereoselectivity.
reductive
radical‐polar
crossover
mechanism,
involving
cascade
XAT,
radical
addition,
1,5‐HAT,
polar
effect‐promoted
5‐endo
annulation,
single
electron
(SET)
reduction,
protonation,
may
account
for
this
unprecedented
dehalogenative
cycloaddition.
This
work
not
only
expands
repertoire
traditional
RATC
methodology,
but
also
provides
robust
platform
expedient
assembly
cyclopentanes,
valuable
structural
motif
realms
medicinal
chemistry
material
sciences.
Science,
Год журнала:
2025,
Номер
388(6744), С. 283 - 291
Опубликована: Апрель 17, 2025
Differentiating
between
similar
alkyl
groups
is
a
major
challenge
in
asymmetric
catalysis.
Achieving
enantiocontrol
over
unactivated
prochiral
radicals
even
more
difficult
owing
to
their
high
reactivity
and
limited
interactions
with
chiral
catalysts.
In
this
study,
we
report
copper-catalyzed
amination
of
secondary
radicals,
using
specifically
designed
anionic
multidentate
ligands
radical
substitution
reaction.
This
approach
efficiently
produces
highly
enantioenriched
α-chiral
amines
facilitates
the
enantioselective
formal
synthesis
series
important
drug
molecules.
Mechanistic
studies
reveal
that
bulky
peripheral
modifications
on
help
create
truncated
cone-shaped
pocket,
enabling
precise
enantiodiscrimination
through
steric
hindrance
noncovalent
interactions.
strategy
holds
broad
potential
for
transformations
involving
diverse
nucleophiles.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 20, 2025
We
have
developed
a
copper-catalyzed
formal
aldehydic
C-H
borylation
using
neutral
sp2-sp3
diboron
reagent,
LBH2-Bpin
(where
L
is
σ-donor),
leading
to
the
one-pot
synthesis
of
diverse
acylboranes.
Notably,
BH
moieties
in
acylborane
can
be
further
used
construct
boracycles.
This
protocol
enables
straightforward
functional
group
(FG)
replacement
commercial
medicines
with
an
acylboron
motif.
Detailed
mechanistic
studies
and
DFT
calculations
reveal
synergistic
hydride
transfer
pathway,
which
promoted
by
electron-rich
nature
LBH2
fragment.
investigation
highlights
potential
new
reagent
accessing
reaction
modes
that
were
previously
unachievable.
Chinese Journal of Chemistry,
Год журнала:
2024,
Номер
42(19), С. 2329 - 2334
Опубликована: Май 22, 2024
Comprehensive
Summary
A
visible
light
photocatalytic
[3+2]
cycloaddition
of
alkynes
with
readily
accessible
organic
iodides
as
the
C3
synthon
is
developed
herein.
By
merging
halogen
atom
transfer
(XAT)
and
hydrogen
(HAT),
alkyl/aryl
serve
a
formal
diradical
precursor
add
across
C‐C
triple
bonds
to
deliver
number
functionalized
cyclopentanes
in
moderate
high
yields
exceptional
regio‐
diastereoselectivity.
reductive
radical‐polar
crossover
mechanism,
involving
cascade
XAT,
radical
addition,
1,5‐HAT,
polar
effect‐promoted
5‐endo
annulation,
single
electron
(SET)
reduction,
protonation,
may
account
for
this
unprecedented
dehalogenative
cycloaddition.
This
work
not
only
expands
repertoire
traditional
RATC
methodology,
but
also
provides
robust
platform
expedient
assembly
cyclopentanes,
valuable
structural
motif
realms
medicinal
chemistry
material
sciences.
