Chinese Journal of Chemistry,
Год журнала:
2024,
Номер
42(24), С. 3243 - 3247
Опубликована: Авг. 24, 2024
Comprehensive
Summary
A
mechanistically
distinctive
visible‐light‐promoted
metal‐free
aerobic
oxidation
of
alkenyl
silanes
with
alcohols
was
disclosed
to
efficiently
construct
α
‐alkoxy
ketones
under
mild
conditions.
The
primary,
secondary,
and
tertiary
could
be
used
as
reactants.
protocol
carried
out
on
a
gram‐scale.
Various
derivatizations
products
conducted.
Mechanistic
studies
indicated
the
reaction
initiated
by
single‐electron
silanes,
rather
than
radical
addition
silanes.
ACS Catalysis,
Год журнала:
2023,
Номер
14(1), С. 418 - 425
Опубликована: Дек. 20, 2023
Miyaura
borylation
is
widely
recognized
as
one
of
the
most
reliable
methods
for
constructing
an
organoboron
compound.
Reported
herein
Pd(0)-catalyzed
asymmetric
three-component
Heck–Miyaura
with
interception
internal
olefin,
aryldiazonium
salt,
and
diboron
reagent.
This
Heck-triggered
protocol
proceeds
in
a
highly
chemoselective,
diastereoselective,
enantioselective
manner,
thus
allowing
expedient
construction
1,2-diaryl
substituted
β-aminoboronate
esters
derivatives
vicinal
stereogenic
centers.
The
versatility
resulting
benzylic
boronic
allows
their
further
transformation
to
more-intricate
chiral
amines.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 3, 2024
The
Barbier
reaction
is
a
reductive-type
addition
of
an
aldehyde
or
ketone
with
organic
electrophile
in
the
presence
terminal
metal
reductant,
providing
straightforward
and
efficient
method
for
carbon-carbon
bond
formation.
This
possesses
advantage
circumventing
preparation
moisture-
air-sensitive
organometallic
reagents.
However,
catalytic
ketones
to
construct
tetrasubstituted
stereogenic
centers
largely
underdeveloped,
despite
its
great
potential
accessing
synthetically
challenging
chiral
tertiary
alcohol.
Particularly,
leveraging
unactivated
alkyl
electrophiles
as
coupling
components
still
rarely
exploited.
Herein,
we
disclose
photoredox-assisted
cobalt-catalyzed
asymmetric
alkylative
Barbier-type
address
aforementioned
challenges,
thereby
allowing
construction
highly
congested
carbon
centers.
fragments
could
be
either
readily
accessible
halides
redox-active
esters
generated
through
decarboxylative
pathway.
Both
types
include
primary,
secondary,
ones,
thus
affording
diverse
enantioenriched
alcohols
broad
substrate
scope.
enantioselective
protocol
applied
expedient
synthesis
core
structure
Angewandte Chemie,
Год журнала:
2024,
Номер
136(25)
Опубликована: Янв. 22, 2024
Abstract
β‐Tertiary
amino
acid
derivatives
constitute
one
of
the
most
frequently
occurring
units
in
natural
products
and
bioactive
molecules.
However,
efficient
asymmetric
synthesis
this
motif
still
remains
a
significant
challenge.
Herein,
we
disclose
cobalt‐catalyzed
enantioselective
reductive
addition
reaction
ketimine
using
α‐chloro
carbonyl
compound
as
radical
precursor,
providing
expedient
access
to
diverse
array
enantioenriched
β‐quaternary
analogues.
This
protocol
exhibits
outstanding
enantioselectivity
broad
substrate
scope
with
excellent
functional
group
tolerance.
Preliminary
mechanism
studies
rule
out
possibility
Reformatsky‐type
confirm
involvement
species
stereoselective
process.
The
synthetic
utility
has
been
demonstrated
through
rapid
assembly
iterative
oligopeptide,
showcasing
its
versatile
platform
for
late‐stage
modification
drug
candidates.
Chemistry - A European Journal,
Год журнала:
2024,
Номер
30(67)
Опубликована: Авг. 13, 2024
Abstract
Difunctionalizations
of
alkenes
represent
one
the
most
straightforward
protocols
to
build
molecular
complexity
due
simultaneous
construction
two
vicinal
bonds
cross
π‐bond
alkenes.
It
is
extremely
attractive
yet
challenging
control
stereochemistry
outcome
this
event.
Over
past
years,
visible‐light
and
Ni‐catalyzed
asymmetric
difunctionalizations
provide
an
environmental
benign
promising
solution
for
saturated
carbon
centers
with
regio‐
enantioselectivity.
In
Concept,
initiative
progress
enantioselective
enabled
by
nickel
catalysis
has
been
summarized.
Moreover,
further
efforts
directions
development
mediated
discussed.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(22), С. 6311 - 6318
Опубликована: Янв. 1, 2024
Co-catalyzed
asymmetric
reductive
addition
of
ketimine
with
cyclopropyl
chloride
has
been
realized
to
access
diverse
chiral
amino
esters
bearing
fragments
broad
functional
group
tolerance
and
excellent
enantioselectivities.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(34)
Опубликована: Июнь 7, 2024
Abstract
A
photocatalyzed
formal
(3+2)
cycloaddition
has
been
developed
to
construct
original
polysubstituted
α‐SCF
3
cyclopentanones
in
a
regio‐
and
diastereoselective
manner.
This
building
block
approach
leverages
trifluoromethylthio
alkynes
branched/linear
aldehydes,
as
readily
available
reaction
partners,
consecutive
hydrogen
atom
transfers
C−C
bond
formations.
Difluoromethylthio
are
also
compatible
substrates.
Furthermore,
the
potential
for
telescoped
starting
from
alcohols
instead
of
aldehydes
was
demonstrated,
well
process
automatization
scale‐up
under
continuous
microflow
conditions.
prompted
density
functional
theory
(DFT)
calculations
support
radical‐mediated
cascade
process.
Chinese Journal of Chemistry,
Год журнала:
2024,
Номер
42(24), С. 3243 - 3247
Опубликована: Авг. 24, 2024
Comprehensive
Summary
A
mechanistically
distinctive
visible‐light‐promoted
metal‐free
aerobic
oxidation
of
alkenyl
silanes
with
alcohols
was
disclosed
to
efficiently
construct
α
‐alkoxy
ketones
under
mild
conditions.
The
primary,
secondary,
and
tertiary
could
be
used
as
reactants.
protocol
carried
out
on
a
gram‐scale.
Various
derivatizations
products
conducted.
Mechanistic
studies
indicated
the
reaction
initiated
by
single‐electron
silanes,
rather
than
radical
addition
silanes.
