Synlett,
Год журнала:
2023,
Номер
35(14), С. 1613 - 1620
Опубликована: Ноя. 15, 2023
Abstract
The
introduction
of
allyl
fluorides
as
alternative
electrophiles
in
asymmetric
allylic
alkylation
reactions
has
recently
attracted
significant
interest.
Despite
the
intrinsic
thermodynamically
demanding
C–F
bond-cleavage
event,
fluorophilic
nature
silicon
atom
is
key
assisting
activation
and
cleavage
bond.
Thus,
use
silylated
compounds
unconventional
nucleophiles,
together
with
Lewis
basicity
fluorine
when
acting
a
leaving
group,
enables
development
innovative
chemical
transformations
within
mild
selective
catalytic
schemes.
This
Synpacts
article
summarizes
diverse
defluorinative
alkylations
reported
to
date
under
both
chiral
base
transition-metal
catalysis.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(40), С. 21752 - 21759
Опубликована: Сен. 28, 2023
Chiral
cyclobutane
presents
as
a
popular
motif
in
natural
products
and
biologically
active
molecules,
its
derivatives
have
been
extensively
used
key
synthons
organic
synthesis.
Herein,
we
report
an
efficient
synthetic
method
toward
enantioenriched
derivatives.
The
reaction
proceeds
cascade
fashion
involving
Ir-catalyzed
asymmetric
allylic
etherification
visible-light
induced
[2
+
2]
cycloaddition.
Readily
available
branched
allyl
acetates
cinnamyl
alcohols
are
directly
the
substrates
under
mild
conditions,
providing
broad
range
of
chiral
cyclobutanes
good
yields
with
excellent
diastereo-
enantioselectivities
(up
to
12:1
dr,
>99%
ee).
It
is
worth
noting
that
all
catalysts
were
simultaneously
added
without
any
separated
step
this
approach.
gram-scale
diverse
transformations
product
further
enhance
potential
utility
method.
ACS Catalysis,
Год журнала:
2024,
Номер
14(9), С. 6687 - 6695
Опубликована: Апрель 16, 2024
The
asymmetric
photoenolization/Diels–Alder
reaction
provides
a
straightforward
and
atom-economical
route
to
complex
chiral
polycyclic
rings.
In
comparison
with
well-developed
transformations
of
2-alkylbenzophenones,
the
enantioselective
2-methylbenzaldehydes
was
challenging
due
shorter-lived
unstable
photoenol
intermediates.
Herein,
we
present
highly
chromones.
Chiral
N,N′-dioxide/ScIII
YbIII
complexes
were
found
interact
both
intermediates
chromones
simultaneously,
accelerating
Diels–Alder
in
an
efficient
stereoselective
manner.
Experimental
studies
DFT
calculations
carried
out
understand
mechanism
origin
stereoselectivity.
addition,
2-alkylbenzophenones
suitable
substrates.
A
series
fused
rings
vicinal
multisubstituted
stereocenters
afforded
good
yields
high
diastereo-
enantioselectivities.
Organic Letters,
Год журнала:
2023,
Номер
25(25), С. 4621 - 4626
Опубликована: Июнь 15, 2023
We
present
here
an
iridium-catalyzed
diastereo-
and
enantioselective
[4
+
1]
cycloaddition
reaction
of
hydroxyallyl
anilines
with
sulfoxonium
ylides
under
mild
conditions,
leading
to
3-vinyl
indolines
in
moderate
good
yields
excellent
enantioselectivities.
Control
experiments
disclosed
a
plausible
mechanism.
Chemical Science,
Год журнала:
2022,
Номер
14(7), С. 1912 - 1918
Опубликована: Дек. 23, 2022
Vinyl-substituted
alcohols
represent
a
highly
useful
class
of
molecular
skeletons.
The
current
method
typically
requires
either
stoichiometric
metallic
reagents
or
preformed
precursors.
Herein,
we
report
nickel
catalysis-enabled
synthesis
vinyl-substituted
via
5-membered
oxa-metallacycle.
In
this
protocol,
acetylene,
the
simplest
alkyne
and
abundant
feedstock,
is
employed
as
an
ideal
C2
synthon.
reaction
features
mild
conditions,
good
functional
group
tolerance
broad
substrate
scope.
Mechanistic
exploration
implies
that
oxa-metallacycle
originated
from
cyclometallation
aldehyde
acetylene
key
intermediate
for
transformation,
which
then
terminated
by
silane-mediated
σ-bond
metathesis
subsequent
reductive
elimination.
Organic Letters,
Год журнала:
2023,
Номер
25(2), С. 325 - 330
Опубликована: Янв. 6, 2023
An
asymmetric
cascade
allylation/spiroketalization
reaction
between
2-(1-hydroxyallyl)phenols
and
5-methyleneoxazolines
is
accomplished
by
using
a
chiral
Ir(I)
catalyst
derived
from
commercially
available
iridium
precursor
the
Carreira
ligand.
This
protocol
furnishes
class
of
structurally
novel
unique
oxazoline-spiroketals
in
up
to
86%
yield,
>99%
ee
>20:1
dr.
Moreover,
control
experiments
reveal
that
4,4-disubstitution
on
necessary
avoid
aromatization
for
spiroketalization
occur.
On
basis
this,
plausible
mechanism
illustrated.
Chemical Science,
Год журнала:
2023,
Номер
14(26), С. 7147 - 7153
Опубликована: Янв. 1, 2023
The
exploitation
of
an
intermolecular
Si–F
interaction
between
the
substrates,
together
with
chiral
Lewis-base
catalysis,
allows
regio-,
diastereo-
and
enantioselective
allylation
ketone-derived
silyl
enol
ethers
allyl
fluorides.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(42), С. 29150 - 29158
Опубликована: Окт. 9, 2024
We
report
herein
the
first
asymmetric
photoinduced
excited-state
Nazarov
reaction
of
non-aromatic
dicyclic
divinyl
ketones
by
using
hydrogen-bonding
catalysis.
The
enantioselectivity
electrocyclization
is
highly
dependent
on
structural
features
substrate
and
its
interaction
with
chiral
catalysts.
For
simple
ketone
substrates,
there
no
discernible
selectivity
hydrogen
bond
coordination
between
thiourea
carbonyl
groups
substrates
in
ground
state.
However,
we
found
that
direction
was
well
controlled
each
model
Accounts of Chemical Research,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 2, 2025
ConspectusPolycyclic
ring
systems
represent
the
most
common
structural
features
of
drug
molecules
and
natural
products.
Chemical
synthesis
complex
polycyclic
with
multiple
stereogenic
centers,
especially
quaternary
carbon
stereocenters,
has
been
a
significant
challenge
in
field
total
synthesis.
Due
to
low
reactivities
substrates
congested
chemical
environments,
efficient
establishment
rings
enantioselective
construction
stereocenters
are
still
ongoing
challenges.
In
our
laboratory,
we
devoted
developing
new
methodologies
strategies
for
syntheses
bioactive
products
exploration
their
biological
potentials.
The
photoenolization/Diels-Alder
(PEDA)
reaction
recognized
as
powerful
strategy
increase
synthetic
efficiency
address
aforementioned
issues.
Over
past
several
years,
group
systematically
reinvestigated
this
terms
its
reactivity
stereoselectivity
developed
unique
dinuclear
metal-promoted
process
constructing
fused
or
spiro
bearing
stereocenters.
During
course
investigation,
have
come
realize
how
rationally
design
route
based
on
PEDA
successfully
implement
projects.In
Account,
summarize
endeavors
journeys
development
application
topologically
order
draw
attention
broad
utility
encourage
further
uptake.
first
part,
provide
details
investigation
issues
reactivity,
diastereoselectivity,
enantioselectivity.
An
involving
Ti(Oi-Pr)4
TADDOL-type
ligands
was
developed.
This
enables
sterically
bulky
dienophiles
interact
transient
photoenolized
hydroxy-o-quinodimethanes,
delivering
wide
range
single
vicinal
good
yields
excellent
enantioselectivities.
second
showcase
potential
tricyclic
systems,
gem-dimethyl
groups
located
at
junction,
were
efficiently
constructed
by
Ti(Oi-Pr)4-promoted
reactions,
which
enabled
three
different
types
products,
including
aromatic
polyketides
(anthrabenzoxocinones,
fasamycins/naphthacemycins,
benastatins),
meroterpenoid
(oncocalyxone
B),
halenaquinones
(xestoquinone,
adociaquinones
A
B).
To
access
structurally
more
triterpenoids,
namely,
perovskones
hydrangenones,
asymmetric
build
along
contiguous
also
applied
achieve
aryltetralin
lactone
lignans.
Furthermore,
an
intramolecular
provides
pathway
rapid
highly
hydrophenanthrene
stereocenter,
facilitating
five
hasubanan
alkaloids.
We
anticipate
that
will
inspire
future
innovations
progressions
photo
be
expanded
applications
molecules.
A
platinum-catalyzed
reaction
of
enynones
with
various
dienophiles
has
been
developed
for
the
construction
tetrahydronaphthalene
derivatives,
which
undergo
a
Diels-Alder
process
platinum
carbenes
and
o-quinone
dimethide
(o-QDM)
intermediates.
In
this
protocol,
an
alkoxy-substituted
conjugated
enynone
is
used
as
nondiazo
carbene
precursor
generation
o-QDMs,
thereby
extending
methods
available
o-QDMs.
The
characterized
by
its
high
atom
economy,
diastereoselectivity,
broad
substrate
scope.
