Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(25)
Опубликована: Апрель 22, 2023
We
report
that
a
nickel
catalyst
system
with
modified
1,1'-spirobiindane-7,7'-diol-phosphoramidite
(SPINOL)
as
the
chiral
ligand
can
enable
coupling
of
tertiary
cyclobutenols
and
arylboroxines
in
an
enantioconvergent
manner,
providing
cyclobutenes
all-carbon
quaternary
stereocenter
good
yields
(up
to
84
%
yield)
excellent
enantioselectivities
>99
ee).
Moreover,
catalytic
be
applied
kinetic
resolution
under
slightly
conditions,
giving
enantioenriched
s
factor
up
>200.
The
reaction
uses
free
hydroxyl
groups
leaving
group
without
additional
activation
while
strained
ring
remains
untouched.
Preliminary
mechanistic
studies
reveal
inherent
discrepant
reactivity
two
enantiomers
is
key
controllable
process.
Science,
Год журнала:
2023,
Номер
381(6653), С. 75 - 81
Опубликована: Июль 6, 2023
Skeletal
ring
enlargement
is
gaining
renewed
interest
in
synthetic
chemistry
and
has
recently
focused
on
insertion
of
one
or
two
atoms.
Strategies
for
heterocyclic
expansion
through
small-ring
remain
elusive,
although
they
would
lead
to
the
efficient
formation
bicyclic
products.
Here,
we
report
a
photoinduced
dearomative
thiophenes
by
bicyclo[1.1.0]butanes
produce
eight-membered
rings
under
mild
conditions.
The
value,
broad
functional-group
compatibility,
excellent
chemo-
regioselectivity
were
demonstrated
scope
evaluation
product
derivatization.
Experimental
computational
studies
point
toward
photoredox-induced
radical
pathway.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(8), С. 5232 - 5241
Опубликована: Фев. 13, 2024
In
pursuit
of
potent
pharmaceutical
candidates
and
to
further
improve
their
chemical
traits,
small
ring
systems
can
serve
as
a
potential
starting
point.
Small
units
have
the
additional
merit
loaded
strain
at
core,
making
them
suitable
reactants
they
capitalize
on
this
intrinsic
driving
force.
With
introduction
cyclobutenone
strained
precursor
ketene,
photocycloaddition
with
another
unit,
bicyclo[1.1.0]butane
(BCB),
enables
reactivity
both
π-units
in
transient
ketene.
This
double
strain-release
driven
[2π+2σ]-photocycloaddition
promotes
synthesis
diverse
heterobicyclo[2.1.1]hexane
units,
pharmaceutically
relevant
bioisostere.
The
effective
under
catalyst-free
conditions
high
functional
group
tolerance
defines
its
synthetic
utility.
Experimental
mechanistic
studies
density
theory
(DFT)
calculations
suggest
that
takes
place
via
triplet
mechanism.
Chemical Science,
Год журнала:
2024,
Номер
15(23), С. 8993 - 8999
Опубликована: Янв. 1, 2024
The
aromatization-driven
deconstructive
coupling
of
spiro
carbocycles
with
organic
halides
via
dual
photoredox/nickel
catalysis
is
developed.
An
in-depth
mechanism
study
revealed
that
this
reaction
proceeded
a
radical-metal
crossover
pathway.
Nature Communications,
Год журнала:
2023,
Номер
14(1)
Опубликована: Авг. 29, 2023
Classical
metalation
reactions
such
as
the
metal-halogen
exchange
have
had
a
transformative
impact
on
organic
synthesis
owing
to
their
broad
applicability
in
building
carbon-carbon
bonds
from
carbon-halogen
bonds.
Extending
logic
metal-carbon
would
enable
direct
modification
of
carbon
frameworks
with
new
implications
retrosynthetic
analysis.
However,
transformation
requires
selective
cleavage
highly
inert
chemical
and
formation
stable
intermediates
amenable
further
synthetic
elaborations,
hence
its
development
has
remained
considerably
challenging.
Here
we
introduce
skeletal
strategy
that
allows
lactams,
prevalent
motif
bioactive
molecules,
be
readily
converted
into
well-defined,
synthetically
useful
organonickel
reagents.
The
reaction
features
activation
unstrained
amide
C-N
mediated
by
an
easily
prepared
Ni(0)
reagent,
followed
CO
deinsertion
dissociation
under
mild
room
temperature
conditions
formal
carbonyl-to-nickel-exchange
process.
underlying
principles
this
unique
reactivity
are
rationalized
organometallic
computational
studies.
is
applied
excision
isotope
underscoring
potential
synthesis.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(32), С. 22829 - 22839
Опубликована: Авг. 1, 2024
The
molecular
editing
of
ketones
represents
an
appealing
strategy
due
to
its
ability
maximize
the
structural
diversity
ketone
compounds
in
a
straightforward
manner.
However,
developing
efficient
methods
for
arbitrary
modification
ketonic
molecules,
particularly
those
integrated
within
complex
skeletons,
remains
significant
challenge.
Herein,
we
present
unique
recasting
that
involves
radical
acylation
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(23)
Опубликована: Апрель 2, 2024
The
diversified
synthesis
of
chiral
fluorinated
cyclobutane
derivatives
has
remained
a
difficult
task
in
synthetic
chemistry.
Herein,
we
present
an
approach
for
asymmetric
hydroboration
and
formal
hydrodefluorination
gem-difluorinated
cyclobutenes
through
rhodium
catalysis,
providing
α-boryl
cyclobutanes
monofluorinated
with
excellent
regio-
enantioselectivity,
respectively.
key
to
the
success
two
transformations
relies
on
efficient,
mild
highly
selective
rhodium-catalyzed
HBPin
(pinacolborane),
which
subsequent
addition
base,
catalytic
amount
palladium
some
cases,
results
formation
products
four-membered
ring
retained.
obtained
are
versatile
building
blocks
that
provide
platform
enantioenriched
great
diversity.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(40), С. 27583 - 27593
Опубликована: Сен. 26, 2024
The
exploration
of
strong
chemical
bonds
as
synthetic
handles
offers
new
disconnection
strategies
for
the
synthesis
functionalized
molecules
via
transition
metal
catalysis.
However,
slow
oxidative
addition
rate
these
covalent
to
a
center
hampers
their
utility.
Here,
we
report
C(sp
Natural Product Reports,
Год журнала:
2024,
Номер
41(2), С. 251 - 272
Опубликована: Янв. 1, 2024
Covering:
2016
to
2023The
synthetic
chemistry
community
is
always
in
pursuit
of
efficient
routes
natural
products.
Among
the
many
available
general
strategies,
skeletal
reorganization,
which
involves
formation,
cleavage,
and
migration
C-C
C-heteroatom
bonds,
stands
out
as
a
particularly
useful
approach
for
assembly
molecular
skeletons.
In
addition,
it
allows
late-stage
modification
products
quick
access
other
family
members
or
unnatural
derivatives.
This
review
summarizes
syntheses
steroid,
terpenoid,
alkaloid
that
have
been
achieved
by
means
this
strategy
past
eight
years.
Our
goal
illustrate
strategy's
potency
reveal
spectacular
human
ingenuity
demonstrated
its
use
development.
