Handbook of CH‐Functionalization,
Год журнала:
2022,
Номер
unknown, С. 1 - 48
Опубликована: Окт. 1, 2022
Abstract
Transition
metal‐catalyzed
transformations
involving
converting
CH
bonds
into
CC
or
CX
bond
have
been
extensively
explored,
which
expedite
the
synthesis
of
target
molecules
via
novel
and
efficient
disconnections
in
retrosynthetic
analysis.
Directing
group‐assisted
activation
is
one
most
used
strategy
to
obtain
site‐selective
functionalization.
Ideal
directing
groups
are
ubiquitously
available,
stable,
easily
removed,
transformable.
Carboxylates
perfectly
meet
with
those
prerequisites.
Carboxylic
acids
widely
exist
organic
molecules,
can
be
tracelessly
removed
by
protodecarboxylation
converted
other
functional
groups.
Thus,
carboxylate‐directed
significant
importance.
Molecules,
Год журнала:
2023,
Номер
28(18), С. 6488 - 6488
Опубликована: Сен. 7, 2023
Multicomponent
reactions
(MCRs)
have
undoubtedly
emerged
as
the
most
indispensable
tool
for
organic
chemists
worldwide,
finding
extensive
utility
in
synthesis
of
intricate
natural
products,
heterocyclic
molecules
with
significant
bioactivity,
and
pharmaceutical
agents.
The
multicomponent
one-pot
1,3-dipolar
cycloaddition
reactions,
which
were
initially
conceptualized
by
Rolf
Huisgen
1960,
find
application
contemporary
chemistry.
In
terms
green
synthesis,
is
highly
favored
owing
to
its
numerous
advantages,
including
high
step-
atom-economies,
remarkable
product
diversity,
well
excellent
efficiency
diastereoselectivity.
Among
pieces
research,
fascinating
reaction
involves
utilization
azomethine
ylides
generated
from
isatins
amino
acids
that
can
be
captured
various
dipolarophiles.
This
approach
offers
a
efficient
convenient
method
constructing
spiro-pyrrolidine
oxindole
scaffolds,
are
crucial
building
blocks
biologically
active
molecules.
Consequently,
this
review
delves
deeper
into
dipolarophiles
utilized
over
past
six
years.
Synthesis,
Год журнала:
2021,
Номер
53(18), С. 3249 - 3262
Опубликована: Июнь 14, 2021
Abstract
Bicyclic
alkenes,
including
oxa-
and
azabicyclic
readily
undergo
activation
with
facial
selectivity
in
the
presence
of
transition-metal
complexes.
This
is
due
to
intrinsic
angle
strain
on
carbon–carbon
double
bonds
such
unsymmetrical
bicyclic
systems.
During
past
decades
considerable
progress
has
been
made
area
ring
opening
strained
rings
by
employing
concept
C–H
activation.
short
review
comprehensively
compiles
various
bond
assisted
reactions
viz.,
ring-opening
reactions,
hydroarylation,
annulation
reactions.
1
Introduction
2
Reactions
Heterobicyclic
Ring
Systems
2.1
Ring-Opening
Oxa-
Azabenzonorbornadienes
2.1.1
Using
7-Oxabenzonorbornadienes
2.1.2
7-Azabenzonorbornadienes
2.2
Hydroarylation
2.3
Annulation
2.4
Other
3
Conclusion
European Journal of Organic Chemistry,
Год журнала:
2021,
Номер
2021(12), С. 1901 - 1908
Опубликована: Март 8, 2021
Abstract
The
mechanism
and
the
origin
of
regioselectivity
rhodium/diene‐catalyzed
ring‐opening
reactions
C1‐substituted
oxabenzonorbornadienes
with
arylboronic
acids
has
been
examined
using
hybrid
density
functional
theory
(DFT).
overall
for
reaction
is
considered
as
a
four‐step
including
transmetalation,
carborhodation,
β‐oxygen
elimination,
protonolysis.
free
energy
profiles
show
that
rate‐determining
step
involved
in
protonolysis
which
differs
from
previous
mechanistic
studies
on
metal‐catalyzed
oxabenzonorbornadienes.
Additionally,
it
theorized
elimination
regioselectivity.
DFT
calculations
predict
formation
1,2,4‐trisubstituted
naphthalene
framework
selective
over
1,1,2‐trisubstituted
product,
agreement
experimental
observations.
Chemical Communications,
Год журнала:
2023,
Номер
59(37), С. 5619 - 5622
Опубликована: Янв. 1, 2023
A
palladium-catalyzed
tandem
reaction
of
7-oxabenzonorbornadienes
with
organic
carboxylic
acids
that
provides
cis-1,2-dihydro-l-naphthyl
derivatives
in
moderate
to
good
yields
a
highly
diastereoselective
manner
is
described.
possible
mechanism
involving
syn
acylation
followed
by
insertion
and
ring-opening
proposed
account
for
the
reaction.
Organic Letters,
Год журнала:
2022,
Номер
24(49), С. 8964 - 8968
Опубликована: Дек. 1, 2022
A
series
of
epoxybenzo[k]fluoranthenes,
epoxy-5H-benzo[b]fluorenes,
and
their
aza
analogues
have
been
accessed
via
palladium-catalyzed
exo-selective
[3
+
2]
annulation
between
aryl
halides
7-oxa-
7-azabenzonorbornadienes.
The
reaction
is
initiated
by
the
oxidative
addition
a
carbon-halogen
bond,
with
intramolecular
C(sp2
or
sp3)-H
activation
being
key
step.
enantioselective
version
was
also
briefly
explored.
Chinese Journal of Organic Chemistry,
Год журнала:
2023,
Номер
43(1), С. 1 - 1
Опубликована: Янв. 1, 2023
In
the
past
two
decades,
transition-metal-catalyzed
keto
carbonyl-directed
C-H
bond
activation
has
evloved
as
a
powerful
and
convenient
tool
for
construction
of
C-C
C-X
(X＝N,
F,
O)
bonds
at
unconventional
reaction
sites
ketones.Among
them,
reactions
catalyzed
by
noble
metals,
involving
ruthenium,
rhodium,
palladium
iridium,
have
been
widely
explored,
whilst
inexpensive
3d
such
manganese,
iron
cobalt,
gradually
emerged
hotspot
catalysts
in
recently.In
this
review,
advances
on
functionalization
from
2014
to
2021
are
summarized,
which
devided
categories
alkylation,
alkenylation,
amidation,
arylation,
cyclization,
so
on.
Chemical Communications,
Год журнала:
2022,
Номер
58(95), С. 13230 - 13233
Опубликована: Янв. 1, 2022
A
regioselective
Rh(III)-catalyzed
C-H
bond
naphthylation
and
cascade
directing
group
(DG)
transformation
has
been
realized
with
aryl
imidates
oxa
bicyclic
alkenes.
Diverse
naphthalene-substituted
aromatic
esters
were
synthesized
fruitfully.
The
DG
into
ester
endows
the
strategy
chances
of
further
functionalization
derivatization.
Preliminary
mechanistic
studies
demonstrate
that
carbonyl
oxygen
possibly
originates
from
corresponding
alkene.
Organometallics,
Год журнала:
2021,
Номер
40(11), С. 1588 - 1597
Опубликована: Май 28, 2021
The
mechanism
and
origins
of
enantio-
stereoselectivity
in
the
asymmetric
ring-opening
(ARO)
reactions
oxabicyclic
alkenes
with
organoboronic
acids
catalyzed
by
rhodium/Josiphos
has
been
examined
at
B3LYP/defTZVP
level
theory.
consists
four
steps
including
transmetalation,
carborhodation,
β-oxygen
elimination,
hydrolysis.
Energetic
discrimination
chirality-imparting
step
arises
from
attractive
C–H−π
interactions
between
transmetalated
aryl
group
Josiphos
ligand,
as
well
steric
clashes
ligand
alkene.
Computational
results
indicate
that
rate-determining
is
involved
hydrolysis
rhodium(I)
alkoxide
ring-opened
intermediate.
In
overall
catalytic
cycle,
greatest
free
energy
barrier
23.4
kcal/mol,
which
supports
Rh-catalyzed
ARO
take
place
mild
reaction
conditions,
consistent
experimental
observations.
Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
365(24), С. 4440 - 4457
Опубликована: Ноя. 22, 2023
Abstract
Oxa(aza)benzonorbornadienes
are
utilized
as
important
synthetic
intermediates
and
useful
building
blocks
in
organic
synthesis
due
to
their
structural
features
reactivity.
In
addition
ring‐opening
reactions,
the
transition‐metal‐catalyzed
ring‐retentive
reactions
of
oxa(aza)bicyclic
alkenes
have
increasingly
drawn
attention
various
researchers.
Numerous
efficient
protocols
this
field
been
investigated
that
enable
facile
transformations
oxa(aza)benzonorbornadienes
related
valuable
adducts,
which
summarized
discussed
detail
review.
