We
report
herein
an
efficient
and
site-selective
electrophilic
trifluoromethylthiolation
of
indolines.
In
the
absence
any
catalyst
or
additive,
C5-selective
could
proceed
at
room
temperature.
With
palladium
used
as
catalyst,
selectivity
was
reversed
completely,
giving
C7-selecive
trifluoromethylthiolated
products.
This
reaction
features
good
functional
group
tolerance,
simple
operation,
mild
conditions,
scale-up
application.
The
potential
utilities
products
were
shown
by
further
transformations.
Chemical Reviews,
Год журнала:
2024,
Номер
124(14), С. 8657 - 8739
Опубликована: Июль 2, 2024
Chiral
phosphorus
ligands
play
a
crucial
role
in
asymmetric
catalysis
for
the
efficient
synthesis
of
useful
optically
active
compounds.
They
are
largely
categorized
into
two
classes:
backbone
chirality
and
P-stereogenic
ligands.
Most
reported
belong
to
former
class.
Privileged
ones
such
as
BINAP
DuPhos
frequently
employed
wide
range
catalytic
transformations.
In
contrast,
latter
class
has
remained
small
family
many
years
mainly
because
their
synthetic
difficulty.
The
late
1990s
saw
emergence
novel
with
superior
enantioinduction
ability
Rh-catalyzed
hydrogenation
reactions.
Since
then,
numerous
have
been
synthesized
used
This
Review
summarizes
thus
far,
including
stereochemical
electronic
properties
that
afford
high
excellent
enantioselectivities.
Examples
reactions
use
this
described
together
applications
construction
key
intermediates
natural
products
therapeutic
agents.
literature
covered
dates
back
1968
up
until
December
2023,
centering
on
studies
published
later
years.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(3), С. 1846 - 1857
Опубликована: Янв. 12, 2024
Herein,
we
describe
an
efficient
transition-metal-free
regioselective
C3alkylation
of
indoles
for
the
synthesis
bis(indolyl)methanes
and
3-styryl
indoles.
Nitrobenzene
is
employed
as
oxidant
to
oxidize
alcohols
in
presence
a
strong
base
reaction
avoids
use
transition
metals
such
Ru
Mn.
The
protocol
provides
favorable
route
access
biologically
active
compounds
arundine,
vibrindole
A,
turbomycin
B.
Organic Process Research & Development,
Год журнала:
2024,
Номер
28(4), С. 949 - 977
Опубликована: Апрель 8, 2024
P-Chiral
phosphorus
ligands
received
little
attention
in
organic
chemistry
until
Knowles
made
his
landmark
contribution
asymmetric
hydrogenation
by
developing
the
P-chiral
CAMP
and
DIPAMP.
The
development
of
accelerated
end
last
century
with
advent
some
highly
efficient
renowned
for
hydrogenation,
including
BisP*,
TangPhos,
QuinoxP*,
DuanPhos,
et
al.
However,
most
reported
were
air-sensitive,
difficult
to
make,
or
lacked
structural
modularity,
hampering
their
availability
applicability.
sterically
electronically
tunable
is
particularly
desirable.
Over
past
decade,
a
family
hindered,
electron-rich,
structurally
tunable,
air-stable
dihydrobenzooxaphosphole
emerged
that
proved
be
versatile
various
transformations.
5
years
witnessed
an
increasing
number
studies
related
these
discovery
unprecedented
catalytic
properties
This
review
highlights
unique
catalysis
applications
synthesis
natural
products
therapeutic
agents.
Organic Letters,
Год журнала:
2024,
Номер
26(7), С. 1483 - 1488
Опубликована: Фев. 12, 2024
Presented
herein
is
a
palladium-catalyzed
asymmetric
(3
+
2)
annulation
reaction
between
1,3-dienes
and
2-formylarylboronic
acids,
proceeding
in
cascade
vinylogous
addition
Suzuki
coupling
process.
Both
electron-neutral
electron-deficient
are
compatible
under
similar
catalytic
conditions,
distinct
regioselectivity
observed
via
functional-group
control
of
1,3-diene
substrates.
A
collection
1-indanols
with
dense
functionalities
constructed
stereoselectively.
Organic Letters,
Год журнала:
2024,
Номер
26(12), С. 2349 - 2353
Опубликована: Март 15, 2024
Enantioselective
construction
of
all-carbon
quaternary
centers
has
been
achieved
via
the
palladium-catalyzed
highly
enantioselective
allenylation
oxindoles
with
2,3-allenylic
carbonates
to
afford
a
variety
optically
active
allene
products,
which
contain
oxindole
units
different
functional
groups,
in
high
ee.
The
corresponding
synthetic
applications
have
also
demonstrated.
Chemical Science,
Год журнала:
2023,
Номер
14(39), С. 10812 - 10823
Опубликована: Янв. 1, 2023
A
class
of
prochiral
allenylic
di-electrophiles
have
been
introduced
for
the
first
time
as
three-atom
synthons
in
cycloadditions,
and
a
new
type
[4+3]
cycloaddition
involving
transition
metal-catalyzed
enantioselective
sequential
substitution
has
successfully
developed,
enabling
challenging
seven-membered
exocyclic
axially
chiral
allenes
to
be
accessed
good
yields
with
enantioselectivity.
Through
addition
catalytic
amount
ortho-aminoanilines
or
ortho-aminophenols,
racemization
products
is
effectively
suppressed.
Mechanistic
studies
reveal
that
elusive
Pd-catalyzed
intramolecular
rather
than
intermolecular
enantio-determining
step
this
cycloaddition.
By
tuning
ligands,
desymmetric
leading
linear
tri-substituted
tandem
substitution/β-vinylic
hydrogen
elimination
(formal
enynylation)
multi-functionalized
1,3-enynes
achieved
chemodivergently.
The
first
catalytic
enantioselective
Friedel-Crafts
(FC)
allenylic
alkylation
for
the
creation
of
central
chirality
has
been
developed
under
cooperative
Ir(I)/(phosphoramidite,olefin)
and
Lewis
acid
catalysis.
Using
racemic
alcohol
as
electrophile,
this
enantioconvergent
reaction
proceeds
through
an
Ir(I)-stabilized
carbocation
intermediate,
which
is
intercepted
with
a
variety
electron-rich
arenes
heteroarenes.
resulting
highly
enantioenriched
(up
to
>99.5:0.5
er)
1,1-disubstituted
methanes,
bearing
benzylic
carbon
stereocenter,
are
obtained
complete
regiocontrol
–
both
on
(hetero)arenes
well
fragment.
This
protocol
allows
formal
introduction
4
alkane
chains
into
stereocenter.
An
intramolecular
version
FC
also
shown
proceed
promising
enantioselectivity
same
conditions.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(7), С. 5200 - 5206
Опубликована: Март 19, 2024
A
regiodivergent
allylation
of
1H-indoles
highly
selectively
at
the
C3
and
N1
positions
with
β-acyl
allylic
sulfides
through
desulfurative
C–C/C–N
bond-forming
reactions
has
been
developed
under
mild
conditions.
Notably,
remarkable
site-selective
switch
can
be
achieved
by
a
delicate
choice
solvents
bases.
This
cost-efficient
method
displays
broad
substrate
scope,
good
functional
compatibility,
excellent
site-selectivity,
thus
offering
divergent
synthesis
indole
substituted
α-branched
enones,
which
possess
diverse
potential
opportunities
for
further
applications
derivatization.
