The Journal of Organic Chemistry,
Journal Year:
2021,
Volume and Issue:
86(3), P. 2827 - 2839
Published: Jan. 20, 2021
A
protocol
for
the
preparation
of
7-amido
indoles
via
regioselective
C–H
bond
functionalization
has
been
first
accomplished
under
Ru(II)
catalysis.
Indole
derivatives
and
4-aryl/heteroaryl/benzyl/alkyl
dioxzaolines
containing
various
substituents
were
applicable
this
transformation,
readily
providing
amidated
in
moderate
to
good
yields.
This
novel
process
many
advantages,
including
compatibility
with
diverse
functional
groups,
broad
substrate
scopes,
mild
reaction
conditions.
Deuteration
studies
control
experiments
have
performed
understand
mechanism
transformation.
Advanced Synthesis & Catalysis,
Journal Year:
2022,
Volume and Issue:
364(13), P. 2113 - 2139
Published: May 6, 2022
Abstract
Olefins
are
important
building
blocks
and
widely
utilized
in
synthetic
organic
chemistry.
Owing
to
its
omnipresence
unique
reactivity,
the
functionalization
of
alkenes
has
become
a
powerful
method
for
constructing
complex
molecules.
In
this
context,
direct
chelation‐assisted
C−H
olefination
at
inert
bonds
represents
most
straightforward
introducing
alkenyl
group
into
compounds
highly
regio‐
stereoselective
manner.
Despite
remarkable
advances
reaction,
successful
transformations
restricted
activated
or
electronically
biased
olefins
such
as
acrylates,
styrenes,
acrylamides,
vinyl
sulfones,
phosphonates.
Literature
reports
on
with
unactivated
unbiased
limited
due
poor
intrinsic
reactivity
regioselectivity
issues.
significant
challenges,
past
few
years
have
witnessed
tremendous
growth.
The
present
review
describes
recent
allylation
aromatics,
alkenes,
heteroaromatics
via
concerted‐metallation‐
deprotonation
pathway.Transition
metals
palladium,
rhodium,
iridium
cobalt
used
these
kind
transformations.
scope,
mechanistic
investigation,
limitation
alkenylation
reactions
discussed
elaborately.
includes
all
reported
base‐assisted
pathway.
magnified
image
Chemical Society Reviews,
Journal Year:
2023,
Volume and Issue:
52(18), P. 6359 - 6378
Published: Jan. 1, 2023
This
review
discusses
the
important
role
of
silver(
i
)
salts
as
additives
in
transition-metal
catalyzed
C–H
activation,
and
depicts
discussion
about
current
shift
towards
Ag-free
procedures,
plausible
sustainable
alternatives.
Organic Letters,
Journal Year:
2020,
Volume and Issue:
22(23), P. 9163 - 9168
Published: Nov. 16, 2020
An
efficient
Rh(III)-catalyzed
C–H
alkenylation/directing
group
migration
cascade
between
indoles
and
alkynes
for
the
assembly
of
tetrasubstituted
alkenes
is
reported.
The
carbamoyl
directing
migrates
to
carbon
alkene
moiety
products
through
rare
Rh-catalyzed
C–N
bond
cleavage
after
alkenylation
step
thus
acts
as
an
internal
amidation
reagent.
This
protocol
shows
broad
substrate
scope,
excellent
regio/stereoselectivity,
good
yields.
Organic Letters,
Journal Year:
2021,
Volume and Issue:
23(2), P. 410 - 415
Published: Jan. 5, 2021
The
indole
scaffold
is
a
ubiquitous
and
useful
substructure,
extensive
investigations
have
been
conducted
to
construct
the
framework
and/or
realize
modification.
Nevertheless,
direct
selective
functionalization
on
benzenoid
core
must
overcome
high
activity
of
C-3
position
still
remains
highly
challenging.
Herein,
palladium-catalyzed
specific
C-7
acylation
indolines
in
presence
an
easily
removed
directing
group
was
developed.
This
strategy
usually
considered
as
practical
for
preparation
acylated
indoles
because
indoline
can
be
converted
under
oxidation
conditions.
In
particular,
our
greatly
improved
alkacylation
yield
which
only
unsatisfactory
could
achieved
previous
studies.
Furthermore,
reaction
scaled
up
gram
level
standard
conditions
with
much
lower
palladium
loading
(1
mol
%).
Organic Letters,
Journal Year:
2021,
Volume and Issue:
23(15), P. 5766 - 5771
Published: July 19, 2021
Herein,
we
report
the
divergent
synthesis
of
alkynylated
imidazo[1,5-a]indoles
and
α,α-difluoromethylene
tetrasubstituted
alkenes
through
Rh(III)-catalyzed
[4
+
1]
annulation/alkyne
moiety
migration
C–H
alkenylation/DG
migration,
respectively.
This
protocol
features
tunable
product
selectivity,
excellent
chemo-,
regio-,
stereoselectivity,
broad
substrate
scope,
moderate
to
high
yields,
good
tolerance
functional
groups,
mild
redox-neutral
conditions.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(31)
Published: May 23, 2022
Transition
metal-catalyzed
C-H
activation
is
a
step-economical
strategy
for
peptide
functionalization.
Herein,
we
report
the
method
of
late-stage
ligation
and
macrocyclization
through
rhodium-catalyzed
alkylation
tryptophan
residues
at
C7
position.
This
utilizes
N-Pt
Bu2
directing
group
tolerates
various
alkene
substrates.
Utilizing
internal
olefins,
this
study
represents
first
example
site-selective
deconjugative
isomerization.
Furthermore,
our
provides
access
to
macrocycles
with
unique
Trp(C7)-alkyl
crosslinks
potent
cytotoxicity
towards
cancer
cells.
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(32), P. 6000 - 6005
Published: Aug. 10, 2022
A
Rh-catalyzed
weak
chelation-guided
C4-alkylation
of
indoles
has
been
accomplished
using
cyclopropanols
as
an
alkylating
agent
via
the
cascade
C–H
and
C–C
bond
activation.
The
substrate
scope,
functional
group
tolerance,
late-stage
mutation
drug
molecules
are
important
practical
features.
Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: July 5, 2023
Abstract
Cyclic
peptides
have
attracted
tremendous
attention
in
the
pharmaceutical
industry
owing
to
their
excellent
cell
penetrability,
stability,
thermostability,
and
drug-like
properties.
However,
currently
available
facile
methodologies
for
creating
such
are
rather
limited.
Herein,
we
report
an
efficient
direct
peptide
cyclization
via
rhodium(III)-catalyzed
C(7)-H
maleimidation.
Notably,
this
catalytical
system
has
regioselectivity
high
tolerance
of
functional
groups
which
enable
late-stage
peptides.
This
architecture
cyclic
exhibits
higher
bioactivity
than
its
parent
linear
Moreover,
Trp-substituted
maleimide
displays
reactivity
toward
Michael
addition,
indicating
potential
as
a
click
group
applications
chemical
biology
medicinal
chemistry.
As
proof
principle,
RGD-GFLG-DOX,
is
peptide-drug-conjugate,
constructed
it
strong
binding
affinity
antiproliferative
activity
integrin-αvβ
3
overexpressed
cancer
lines.
The
proposed
strategy
rapid
preparation
stapled
would
be
robust
tool
peptide-drug
conjugates.
