ACS Catalysis,
Journal Year:
2022,
Volume and Issue:
12(21), P. 13411 - 13417
Published: Oct. 18, 2022
The
intermolecular
1,3-diamination
reaction
of
readily
available
alkenes
with
N-fluorobis(benzenesulfonamides)
catalyzed
by
rhodium(II)
is
reported
herein.
isomers
the
terminal
and
internal
alkenes,
even
mixtures,
all
provided
same
allylic
1,3-diamine
products
under
mild
conditions.
resulting
diaminated
can
be
derived
to
functionalized
diamines
further
generate
triamines.
Mechanistic
studies
revealed
that
compounds
a
variety
chemical
transformations
during
reactions
based
on
their
single-electron
redox
catalytic
cycle,
specifically
radical
polarity
crossover
in
direct
activation
C–H
bonds
followed
cross-coupling
alkenes.
These
results
show
potential
amination
addition
well-known
rhodium
nitrenoids.
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(42), P. 7796 - 7800
Published: Oct. 20, 2022
We
herein
report
a
copper-catalyzed
formal
[5
+
2]
aza-annulation
of
N-fluorosulfonamides
and
1,3-dienes/1,3-enynes
for
synthesis
structurally
diverse
alkene/alkyne-containing
azepanes.
The
reaction
features
selective
functionalization
distal
unactivated
C(sp3)–H
bonds
broad
substrate
scope,
thus
allowing
the
late-stage
modification
pharmaceuticals
natural
products.
A
radical
mechanism
involving
1,5-hydrogen
atom
transfer
N-radicals,
facile
coupling
alkyl
radicals
with
1,3-dienes/1,3-enynes,
construction
azepane
motifs
via
C–N
bond
formation
is
proposed.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(30), P. 5574 - 5578
Published: July 25, 2023
The
1,1,1,3,3,3-hexafluoro-2-propanol-assisted
allenamide
activation
enables
metal-free
regioselective
intermolecular
interception
of
amines,
constituting
a
general
C-N
bond
formation
process
for
accessing
value-added
1,3-diamines.
Exclusive
N-chemoselectivity
(vs
C
anilines)
and
regioselectivity
were
achieved
broad
range
substrates.
Late-stage
modification
further
transformations
the
1,3-diamine
products
showcased
practicability
benefits
this
strategy.
Experimental
mechanistic
studies
revealed
that
1,1,1,3,3,3-hexafluoro-2-propanol
mediates
proton
transfer
allenamide.
Density
functional
theory
computations
role
NaOAc
in
reactive
electrophilic
intermediate,
which
ultimately
governs
selective
product.
Organic Chemistry Frontiers,
Journal Year:
2023,
Volume and Issue:
10(13), P. 3275 - 3279
Published: Jan. 1, 2023
Allylic
C(sp
3
)–H
alkylation
of
α-alkylstyryl
sulfonium
salts
based
on
[2,3]-sigmatropic
rearrangement
strategies
has
been
developed.
This
protocol
could
allow
facile
access
to
allylated
carbon
quaternary
centers
in
moderate
good
yields.
Angewandte Chemie,
Journal Year:
2021,
Volume and Issue:
133(21), P. 11885 - 11889
Published: March 4, 2021
Abstract
Direct
allylic
C−H
thiolation
is
straightforward
for
C(sp
3
)−S
bond
formation.
However,
strong
interactions
between
thiol
and
transition
metal
catalysts
lead
to
deactivation
of
the
catalytic
cycle
or
oxidation
sulfur
atom
under
oxidative
condition.
Thus,
direct
)−H
has
proved
difficult.
Represented
herein
an
exceptional
direct,
efficient,
atom‐
step‐economic
S−H
visible
light
irradiation.
Radical
trapping
experiments
electron
paramagnetic
resonance
(EPR)
spectroscopy
identified
radical
thiyl
generated
on
surface
photocatalyst
quantum
dots
(QDs).
The
C−S
formation
does
not
require
external
oxidants
initiators,
hydrogen
(H
2
)
produced
as
byproduct.
When
vinylic
was
used
instead
bond,
radical‐radical
cross‐coupling
achieved
with
liberation
H
.
Such
a
unique
transformation
opens
up
door
toward
coupling
valuable
organosulfur
chemistry.
ACS Catalysis,
Journal Year:
2022,
Volume and Issue:
12(21), P. 13411 - 13417
Published: Oct. 18, 2022
The
intermolecular
1,3-diamination
reaction
of
readily
available
alkenes
with
N-fluorobis(benzenesulfonamides)
catalyzed
by
rhodium(II)
is
reported
herein.
isomers
the
terminal
and
internal
alkenes,
even
mixtures,
all
provided
same
allylic
1,3-diamine
products
under
mild
conditions.
resulting
diaminated
can
be
derived
to
functionalized
diamines
further
generate
triamines.
Mechanistic
studies
revealed
that
compounds
a
variety
chemical
transformations
during
reactions
based
on
their
single-electron
redox
catalytic
cycle,
specifically
radical
polarity
crossover
in
direct
activation
C–H
bonds
followed
cross-coupling
alkenes.
These
results
show
potential
amination
addition
well-known
rhodium
nitrenoids.
