Journal of the American Chemical Society,
Journal Year:
2021,
Volume and Issue:
143(17), P. 6407 - 6412
Published: April 26, 2021
A
catalytic
intermolecular
amination
of
nonactivated
tertiary
C(sp3)–H
bonds
(BDE
96
kcal·mol–1)
is
reported
for
substrates
displaying
an
activated
benzylic
site
85
kcal·mol–1).
The
bond
selectively
functionalized
to
afford
α,α,α-trisubstituted
amides
in
high
yields.
This
unusual
site-selectivity
results
from
the
synergistic
combination
Rh2(S-tfpttl)4,
a
rhodium(II)
complex
with
well-defined
pocket,
tert-butylphenol
sulfamate
(TBPhsNH2),
which
leads
discriminating
rhodium-bound
nitrene
species
under
mild
oxidative
conditions.
system
very
robust,
and
reaction
was
performed
on
50
mmol
scale
only
0.01
mol
%
catalyst.
TBPhs
group
can
be
removed
conditions
corresponding
NH-free
amines.
Science Advances,
Journal Year:
2025,
Volume and Issue:
11(8)
Published: Feb. 21, 2025
Glycosylation
chemistry
plays
a
pivotal
role
in
glycoscience.
Recent
substantial
developments
have
poised
the
field
to
address
emerging
challenges
related
sustainability,
cost
efficiency,
and
robust
applicability
complex
substrate
settings.
The
transition
from
stoichiometric
activation
metal-catalyzed
methods
promises
enhanced
chemoselectivity
greater
precision
controlling
glycosidic
bond
breakage
formation,
key
overcoming
existing
obstacles.
Here,
we
report
nitrene-mediated
glycosylation
strategy
using
regular
aryl
sulfide
glycosyl
donors
easily
accessible
3-methyl
dioxazolone
as
an
activator
under
catalysis
of
iron
or
ruthenium.
iron-catalyzed
system
demonstrates
exceptional
catalytic
reactivity,
requiring
little
0.1
mole
%
catalyst
at
room
temperature,
works
well
for
peptide
substrates.
ruthenium-catalyzed
can
accommodate
acid-sensitive
functional
groups
challenging
low-reactivity
acceptors.
Mechanistic
investigations
unveiled
unusual
multistep
pathways
involving
sulfur
imidation
via
nitrene
transfer
sulfur-to-oxygen
rearrangement
N-acyl
sulfilimines
donors.
Chemical Communications,
Journal Year:
2021,
Volume and Issue:
57(35), P. 4259 - 4262
Published: Jan. 1, 2021
In
this
work,
by
usingN-methoxybenzamides
as
efficient
acyl
nitrene
precursors,
an
iron-catalyzed
nitrene/alkyne
metalation-based
chloramidation
is
reported
for
the
synthesis
of
isoindol-5-ones.
ACS Catalysis,
Journal Year:
2021,
Volume and Issue:
11(14), P. 8585 - 8590
Published: June 30, 2021
Herein,
we
report
a
Rh(III)-catalyzed
three-component
carboamination
of
alkenes
from
readily
available
aryl
boronic
acids
as
carbon
source
and
dioxazolones
nitrogen
electrophiles.
This
protocol
provides
facile
access
to
valuable
amine
products
including
α-amino
acid
derivatives
in
good
yield
regioselectivity
without
the
need
for
directing
functionality.
A
series
experiments
suggest
mechanism
which
Rh(III)
catalyst
undergoes
transmetalation
with
acid,
followed
by
turnover
limiting
alkene
migratory
insertion
into
Rh(III)-aryl
bond.
Subsequently,
fast
Rh-nitrene
formation
syn-carboamination
product
selectively
after
reductive
elimination
proto-demetalation.
Importantly,
coupling
preference
variety
two-component
undesired
byproducts.
Journal of the American Chemical Society,
Journal Year:
2021,
Volume and Issue:
143(17), P. 6407 - 6412
Published: April 26, 2021
A
catalytic
intermolecular
amination
of
nonactivated
tertiary
C(sp3)–H
bonds
(BDE
96
kcal·mol–1)
is
reported
for
substrates
displaying
an
activated
benzylic
site
85
kcal·mol–1).
The
bond
selectively
functionalized
to
afford
α,α,α-trisubstituted
amides
in
high
yields.
This
unusual
site-selectivity
results
from
the
synergistic
combination
Rh2(S-tfpttl)4,
a
rhodium(II)
complex
with
well-defined
pocket,
tert-butylphenol
sulfamate
(TBPhsNH2),
which
leads
discriminating
rhodium-bound
nitrene
species
under
mild
oxidative
conditions.
system
very
robust,
and
reaction
was
performed
on
50
mmol
scale
only
0.01
mol
%
catalyst.
TBPhs
group
can
be
removed
conditions
corresponding
NH-free
amines.
