Green Synthesis and Catalysis,
Год журнала:
2023,
Номер
unknown
Опубликована: Ноя. 1, 2023
An
environmentally
friendly,
highly
atom-economical
and
operationally
simple
approach
toward
the
synthesis
of
naphtho-fused
2-aminoindolines
naphthoxindoles
starting
from
biaryl
aldehydes
secondary
amines
has
been
developed.
This
notable
methodology
integrates
consecutive
intramolecular
Mannich-type
cyclization
triggered
by
dearomatization
indole
with
subsequent
aromatization
via
β-elimination
then
amination
or
oxidation
at
C2-position
nucleus.
The
amine-controlled
divergent
protocol
together
an
easy
product
isolation
process
provides
a
practical
route
for
first
time
to
access
2-substituted
indoline.
Organic Letters,
Год журнала:
2023,
Номер
25(14), С. 2432 - 2437
Опубликована: Апрель 5, 2023
An
unprecedented
hydride
transfer-triggered
cross-dehydrogenative
coupling
of
two
C(sp3)-H
bonds
to
target
nine-membered
rings
has
been
developed.
Salient
features
this
methodology
include
atom
and
step
economy
metal-free
redox-neutral
conditions,
with
water
as
the
byproduct
proceeding
well
even
decomposed
aldehydes.
Bulletin of the Chemical Society of Japan,
Год журнала:
2022,
Номер
95(2), С. 296 - 305
Опубликована: Янв. 12, 2022
Abstract
An
efficient
catalytic
internal
redox
reaction
(hydride
shift
mediated
C(sp3)–H
bond
functionalization)
has
been
developed,
which
the
following
salient
features:
(1)
functionalization,
(2)
Lewis
and/or
Brønsted
acid
catalyzed
(transition
metals
employed
in
conventional
C–H
functionalization
are
not
required),
and
(3)
construction
of
complex
polycycles
that
otherwise
difficult
to
synthesize
by
methods.
Our
recent
efforts
on
development
novel
types
hydride
shift/cyclization
system
described.
Organic Letters,
Год журнала:
2021,
Номер
23(24), С. 9403 - 9407
Опубликована: Ноя. 30, 2021
We
have
achieved
a
divergent
access
to
seven/five-membered
rings
based
on
[1,6]-hydride
shift/cyclization
process
from
benzylidenemalonate
with
an
o-alkoxymethyl
group.
Whereas
Yb(OTf)3
afforded
benzoxepines
(with
seven-membered
ring)
selectively,
indanes
five-membered
were
the
main
products
when
Sc(OTf)3
was
employed.
Frontiers in Chemistry,
Год журнала:
2022,
Номер
10
Опубликована: Апрель 7, 2022
The
direct
functionalization
of
inert
C–H
bonds
is
regarded
as
one
the
most
powerful
strategies
to
form
various
chemical
and
construct
complex
structures.
Although
significant
advancements
have
been
witnessed
in
area
transition
metal-catalyzed
bonds,
several
challenges,
such
utilization
removal
expensive
metal
complexes,
limited
substrate
scope
large-scale
capacity,
poor
atom
economy
removing
guiding
groups
coordinated
metal,
cannot
fully
fulfill
high
standard
modern
green
chemistry
nowadays.
Over
past
decades,
due
its
inherent
advantage
compared
with
a
strategy,
hydride
shift
activation
that
applies
“
tert
-amino
effect”
into
common
omnipresent
C(sp
3
)–H
adjacent
-amines
has
attracted
much
attention
from
chemists.
In
particular,
intramolecular
[1,5]-hydride
activation,
mode,
enables
rapid
effective
production
multifunctionally
frameworks,
especially
spiro-tetrahydroquinoline
derivatives,
which
are
widely
found
biologically
active
natural
products
pharmaceuticals.
great
accomplishments
achieved
this
promising
field,
rarely
an
updated
review
systematically
summarized
these
important
progresses
despite
scattered
reports
documented
reviews.
Hence,
review,
we
will
summarize
advances
cascade
shift/intramolecular
)-H
perspective
build
skeleton,
content
categorized
by
structure
type
final
containing
pharmaceutical
units.
Besides,
current
limitations
well
future
directions
field
also
pointed
out.
We
hope
our
could
provide
quick
look
offer
some
inspiration
for
research
on
strategy
future.
The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
88(2), С. 1061 - 1074
Опубликована: Янв. 11, 2023
An
iodine-mediated
intramolecular
sp3
C-H
amination
reaction
producing
quinazolinone-fused
polycyclic
skeletons
from
2-aminobenzamide
precursors
is
reported.
This
does
not
use
transition
metals,
has
a
broad
substrate
scope,
and
can
be
used
on
gram
scale.
Under
the
optimal
conditions,
variety
of
tetrahydroisoquinolines
derivatives
Rutaecarpine
were
synthesized
readily
accessible
compounds.
The
proceeds
well
with
crude
derivatives,
allowing
for
synthesis
products
simple
2-aminobenzoic
acids
without
purification
intermediates.
Preliminary
biological
experiments
have
identified
Cereblon
(CRBN)
inhibitory
activity
relevant
anti-myeloma
medicinal
properties
in
some
these
products.
The
[1,n]-hydride
migration
reactions
represent
one
of
the
most
powerful
techniques
to
functionalize
C(sp3)–H
bonds
and
rapidly
construct
molecular
complexities.
However,
their
substrates
usually
required
multiple
steps
prepare
in
advance.
Herein,
we
developed
a
gold-catalyzed
intermolecular
coupling
hydride-donor-containing
nucleophiles
(amines)
hydride-acceptor-containing
alkynes
(1,3-diynamides)
for
cascade
[1,5]-hydride
migrations.
Control
experiments
revealed
role
dichloroethane
solvent
unexpected
involvement
protonated
anilines
promoting
Herein,
for
the
first
time,
controllable,
accurate,
and
diverse
synthesis
of
all
ring
sizes
medium-sized
(8-
to
11-membered)
indole-derived
bridged
biaryls
has
been
realized
by
using
ingeniously
designed
o-alkynylnaphthols
that
feature
cyclic
amines
with
adjustable
sizes.
The
transformation
may
proceed
through
a
DBN-mediated
in-situ
generation
vinylidene
ortho-quinone
methides/indole-ring
formation/ring
expansion
cascade
sequence,
which
is
characterized
acceptable
excellent
yields
good
functional
group
tolerance.
Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
365(4), С. 502 - 507
Опубликована: Фев. 2, 2023
Abstract
We
have
developed
a
sequential
hydride
shift
process
involving
[1,8]‐hydride
shift.
When
cinnamylidene
malonates
having
biphenyl
core
were
treated
with
30
mol%
Yb(OTf)
3
and
10
i
Pr
2
NEt,
the
desired
[1,8]‐[1,5]‐hydride
proceeded
smoothly
to
afford
synthetically
challenging
nine‐membered
carbocycle‐fused
piperidine
derivatives
in
good
chemical
yields
(up
77%).
Notably,
carbocycles
could
not
be
obtained
by
single
shift/cyclization
process,
suggesting
that
employment
of
system
is
crucial
achieving
reaction.
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