Synthesis of α-Substituted Cyclic Boronates via Titanium-Catalyzed Cyclization of Vinyl Boronates with Dihaloalkanes
Chemical Science,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
A
titanium-catalyzed
reductive
cyclization
of
vinyl
boronates
with
gem
-dihaloalkanes
is
developed.
α-Substituted
cyclic
that
are
otherwise
difficult
to
access,
such
as
those
heteroatom-containing
rings,
readily
obtained.
Язык: Английский
Trendbericht: Organische Chemie 2025
Nachrichten aus der Chemie,
Год журнала:
2025,
Номер
73(3), С. 40 - 70
Опубликована: Фев. 28, 2025
Abstract
Highlights
von
November
2023
bis
2024:
die
erste
Einelektron‐C–C‐σ‐Bindung
und
Anti‐Bredt‐Verbindung;
gesättigte
Heterocyclen
elektrochemisch
funktionalisieren;
Ausrichten
diskotischer
Flüssigkristalle;
enantioselektive
Wagner‐Meerwein‐Umlagerung
reiner
Aliphaten;
photokatalytisch
Furanen
zu
Pyrrolen;
mit
Ammoniak
primären
Arylaminen;
Metallschrott
recyceln
ionischen
Flüssigkeiten;
terminale
Alkene
Ni‐Katalysatoren
zum
(Z)‐
oder
(E)‐Alken
isomerisieren;neue
Fungizide,
Medikamente
Alkaloide.
Empowering Diastereoselective Cyclopropanation of Unactivated Alkenes with Sulfur Ylides through Nucleopalladation
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 7, 2025
Regio-
and
stereoselective
cyclopropanation
of
unactivated
alkenes
under
mild
conditions
remains
a
challenging
yet
fundamental
transformation.
We
present
versatile
palladium(II)-catalyzed
method
for
the
diastereoselective
alkenyl
amines
acids,
which
leverages
nucleopalladation
mechanism
unique
ambiphilic
reactivity
sulfur
ylides.
This
Pd(II)/Pd(IV)
catalytic
protocol
selectively
delivers
anti-cyclopropanes
allylamines
with
removable
isoquinoline-1-carboxamide
auxiliary,
while
enabling
excellent
syn-selectivity
acid
derivatives
containing
2-(aminomethyl)pyridine
derivative
as
directing
group.
The
is
operationally
simple
scalable,
features
wide
substrate
generality,
also
effective
in
presence
various
medicinally
relevant
scaffolds.
cyclopropane
products
were
further
transformed
into
1,2,3-trifunctionalized
cyclopropanes
engaged
an
aza-Piancatelli
reaction,
introducing
additional
molecular
complexity.
DFT
studies
performed
to
shed
light
on
reaction
origins
observed
stereoselectivity.
Язык: Английский
Rh-Catalyzed Enantioselective Aryl C–H Bond Cyclopropylation
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 10, 2025
Herein,
we
disclose
the
discovery
and
development
of
a
site-,
regio-,
diastereo-,
enantioselective
aryl
C-H
bond
cyclopropylation
using
diazomethyl
hypervalent
iodine
reagents,
styrenes,
paddlewheel
dirhodium
carboxylate
catalysts.
A
key
aspect
this
work
was
catalytic
generation
chiral
Rh(II)
carbene
through
an
electrophilic
aromatic
substitution
with
carbynoids.
The
strategy
allows
construction
cyclopropane
rings
bonds
from
feedstocks
drug
molecules
promises
to
reach
unexplored
"cyclopropanated"
chemical
space
highly
difficult
by
current
strategies.
Язык: Английский
Safer and cheaper ways to carbenes
Nachrichten aus der Chemie,
Год журнала:
2025,
Номер
73(5), С. 80 - 84
Опубликована: Апрель 30, 2025
Abstract
Metal
carbenes
are
involved
in
cycloadditions,
metatheses
and
C–H
functionalizations.
However,
their
main
precursors
hazardous
diazo
compounds,
which
makes
them
unfit
for
industrial
use.
Recently,
however,
synthetic
strategies
overcame
this
limitation
—
enabling
access
to
metal
from
aldehydes,
carboxylic
acids
alcohols.
Язык: Английский
Catalytic Aldehyde–Alkyne Couplings Triggered by Ketyl Radicals
Organic Letters,
Год журнала:
2024,
Номер
26(46), С. 9949 - 9954
Опубликована: Ноя. 8, 2024
A
general
and
flexible
platform
for
catalytic
aldehyde-alkyne
couplings
triggered
by
ketyl
radicals
is
described.
This
open-shell
strategy
necessitates
only
a
quantity
of
photoredox
catalyst,
along
with
Hünig's
base
(DIPEA)
as
halogen
atom
transfer
reagent.
The
reaction
proceeds
through
sequential
steps
involving
activation,
transfer,
radical
addition.
carbonyl-alkyne
coupling
exhibits
wide
substrate
scope
functional
group
compatibility
has
been
successfully
applied
to
the
late-stage
modification
complex
architectures.
Язык: Английский