An
organocatalytic
annulative
sulfur(VI)-fluoride
exchange
(SuFEx)
reaction
of
β-arylethenesulfonyl
fluorides
has
been
reported.
Under
the
catalysis
10
mmol%
BTMG
and
molecular
sieves
4Å,
undergo
Michael
addition-intramolecular
SuFEx
click
with
benzofuran-3(2H)-ones
to
give
δ-sultone-fused
benzofurans
in
76-99%
yield.
Using
DBU
coupled
oxindoles
produce
indoles
81-85%
In
these
reactions,
4Å
act
as
efficient
HF
scavenger,
which
avoid
using
stoichiometric
silicon
additives
bases.
Importantly,
density
functional
theory
(DFT)
calculations
reveal
that
addition
is
a
decisive
speed
step
for
reaction.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 2, 2025
Regiodivergent
asymmetric
synthesis
represents
a
transformative
strategy
for
the
efficient
generation
of
structurally
diverse
chiral
products
from
single
set
starting
materials,
significantly
enriching
their
enantiomeric
composition.
However,
design
radical-mediated
regiodivergent
and
enantioselective
reactions
that
can
accommodate
wide
range
functional
groups
substrates
has
posed
significant
challenges.
The
obstacles
primarily
lie
in
switching
regioselectivity
achieving
high
enantiodiscrimination,
especially
when
dealing
with
high-energy
intermediates.
To
address
these
issues,
we
have
developed
new
catalytic
system
integrates
photoinduced
hydrogen
atom
transfer
(HAT)
copper
catalysis,
involving
fine-tuning
ligands,
additives,
other
reaction
parameters.
facilitates
cross-couplings
between
N-aryl
glycine
ester/amide
derivatives
abundant
hydrocarbon
feedstocks
through
strong
C(sp3)–H
bond
activation.
This
approach
allows
controlled
stereoselective
formation
C(sp3)–C(sp3)
C(sp3)–N
bonds,
yielding
rich
variety
C-
or
N-alkylated
esters
amides
commendable
yields
(up
to
92%
yield),
exclusive
regioselectivities
(typically
>20:1
rr),
enantioselectivities
96%
ee).
Our
methodology
not
only
provides
promising
avenue
incorporation
alkyl
functionalities
onto
specific
sites
biologically
molecules
but
also
offers
practical
while
simultaneously
induction
within
photochemical
reactions.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(16), С. 4391 - 4401
Опубликована: Янв. 1, 2024
The
mechanism
and
origin
of
regio-
diastereoselectivity
in
the
reaction
divergent
[3
+
2]
annulation
aliphatic
aldimines
with
alkenes
by
scandium-catalyzed
β-C(sp
3
)–H
activation
have
been
revealed
detail
using
DFT
calculations.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(10), С. 2905 - 2910
Опубликована: Янв. 1, 2024
A
chiral
bifunctional
Brønsted
base-catalyzed
enantioselective
[3
+
2]
cycloaddition
of
D–A
cyclopropanes
and
azadienes
is
reported.
The
protocol
features
broad
substrate
scope,
mild
reaction
conditions
high
functional
group
tolerance.
RSC Advances,
Год журнала:
2025,
Номер
15(14), С. 10634 - 10638
Опубликована: Янв. 1, 2025
The
transition-metal-free
regioselective
[3
+
2]
annulation
of
azadienes
with
haloalcohols
for
the
preparation
highly
functionalized
spiro-oxazolidines
is
experimentally
simple,
broad
substrate
scope,
good
yields,
and
excellent
regioselectivity.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(20), С. 15271 - 15281
Опубликована: Окт. 10, 2024
Chiral
bifunctional
thiourea-catalyzed
Diels-Alder
reaction
between
olefinic
azlactones
and
alkylidene
thiazolone
derivatives
is
reported
here
for
the
first
time.
The
asymmetric
delivers
vicinal
tertiary-quaternary
stereocenters
in
spirocyclohexenone
thiazolones
moderate
to
high
yields
good
stereochemical
outcomes.
protocol
can
be
adapted
a
broad
array
of
substrates.
Moreover,
scaled
up,
chiral
was
converted
into
valuable
spirocyclic-1,2-amidoalcohol
highlighting
synthetic
utility
our
methodology.
Organic Letters,
Год журнала:
2024,
Номер
26(15), С. 3235 - 3240
Опубликована: Апрель 1, 2024
Catalytic
asymmetric
1,2-allylation
of
aurone-derived
azadienes
is
very
difficult
to
achieve
due
the
driving
force
for
aromatization
and
greater
steric
hindrance
1,2-addition
compared
with
1,4-addition.
By
taking
advantage
ability
nitrogen
ligated
metal
complexes,
we
successfully
demonstrated
first
example
copper-catalyzed
allylboronates
highly
enantioselective
synthesis
homoallylic
amines.
Meanwhile,
enantioenriched
1,4-addition
products
could
also
be
obtained
through
a
subsequent
3,3-sigmatropic
rearrangement
products.
Extensive
DFT
calculations
were
carried
out
elucidate
origins
high
regioselectivity
(1,2-
vs
1,4-)
enantioselectivity.
Organic & Biomolecular Chemistry,
Год журнала:
2023,
Номер
22(2), С. 252 - 268
Опубликована: Ноя. 28, 2023
Eight-membered
heterocycles
are
important
but
their
synthesis
is
usually
challenging.
This
review
summarizes
the
recent
advances
in
[4
+
4]
annulation
of
conjugated
heterodienes
with
1,4-dipolar
species
for
assembling
eight-membered
heterocycles.
Organic & Biomolecular Chemistry,
Год журнала:
2024,
Номер
22(34), С. 7039 - 7051
Опубликована: Янв. 1, 2024
A
transition
metal-free
approach
has
been
devised
for
the
synthesis
of
a
variety
bis(indolyl)propyne
(BIP)
derivatives.
The
strategy
involves
an
iodine-catalyzed
cascade
condensation
α,β-unsaturated
acetylenic
aldehydes
with
diversely
substituted
indoles.
was
applicable
to
gram
scale
and
library
50
molecules,
which
were
afforded
in
good
excellent
yields
(up
96%),
developed.
salient
features
reaction
involve
indole
based
privileged
scaffolds
short
time
under
conditions,
wide
substrate
scope
ambient
conditions.
