Facile Synthesis of Housanes by an Unexpected Strategy
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 17, 2025
Rigid
bicyclic
hydrocarbons
have
emerged
as
important
building
blocks
in
the
drug
discovery
industry.
Despite
progress
this
general
area,
bicyclo[2.1.0]pentanes
(housanes)
are
an
understudied
class
of
molecules.
Herein
we
report
unconventional
synthesis
borylated
housanes.
Our
method
features
a
broad
scope
and
high
diastereoselectivities
versatile
intermediates.
The
route
involves
strain-release
diboration
bicyclo[1.1.0]butane
intramolecular
deborylative
alkylation.
versatility
bridgehead
boronic
ester
was
demonstrated
several
functionalizations.
Lastly,
mechanism
reaction
investigated,
unusual
stereospecific
diastereoselective
ring
expansion
uncovered.
Язык: Английский
Palladium‐Catalyzed Cascade Heck Coupling and Allylboration of Iododiboron Compounds via Diboryl Radicals
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(18)
Опубликована: Март 6, 2024
Geminal
bis(boronates)
are
versatile
synthetic
building
blocks
in
organic
chemistry.
The
fact
that
they
predominantly
serve
as
nucleophiles
the
previous
reports,
however,
has
restrained
their
potential.
Herein
we
disclose
ambiphilic
reactivity
of
α-halogenated
geminal
bis(boronates),
which
first
catalytic
utilization
was
accomplished
by
merging
a
formal
Heck
cross-coupling
with
highly
diastereoselective
allylboration
aldehydes
or
imines,
providing
new
avenue
for
rapid
assembly
polyfunctionalized
boron-containing
compounds.
We
demonstrated
this
cascade
reaction
is
efficient
and
compatible
various
functional
groups,
wide
range
heterocycles.
In
contrast
to
classical
Pd(0/II)
scenario,
mechanistic
experiments
DFT
calculations
have
provided
strong
evidence
cycle
involving
Pd(I)/diboryl
carbon
radical
intermediates.
Язык: Английский
Boron Ylide Enables Stereoselective Construction of gem‐Diborylcyclopropanes
Tongchang Fang,
Peng Zhang,
Chao Liu
и другие.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 20, 2024
Abstract
The
stereoselective
cyclopropanation
of
olefins
with
“boron
ylide”
is
disclosed
for
the
first
time,
providing
a
modular
strategy
synthesis
stereospecific
diboryl‐functionalized
cyclopropanes.
chiral
gem
‐diborylcyclopropanes
are
synthesized
excellent
enantioselectivity
aid
auxiliary.
Based
on
powerful
transformable
ability
boryl
group,
those
challenging
multi‐quaternary
carbon
centers
in
cyclopropane
units
have
been
facilely
constructed
stereoselectivity.
Control
experiments
indicate
that
groups
necessary
both
chemoselectivity
and
stereoselectivity
control.
Язык: Английский
Synthesis of 1,4-Diketones from Esters Enabled by a Tetraborylethane Reagent
Organic Letters,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 25, 2025
A
modular
synthesis
method
for
1,4-diketones
has
been
developed.
Utilizing
inexpensive
carboxylic
acid
esters
as
carbonyl
sources
and
tetraborylethane
(TBE)
a
nucleophilic
reagent,
one-pot
strategy
constructing
two
C-C
bonds
was
established.
Notably,
this
reaction
proceeds
without
the
involvement
of
transition
metals
exhibits
excellent
functional
group
compatibility.
diverse
array
α-substituted
were
synthesized
using
various
electrophiles
capture.
Язык: Английский
Boron Ylide Enables Stereoselective Construction of gem‐Diborylcyclopropanes
Tongchang Fang,
Peng Zhang,
Chao Liu
и другие.
Angewandte Chemie,
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 20, 2024
Abstract
The
stereoselective
cyclopropanation
of
olefins
with
“boron
ylide”
is
disclosed
for
the
first
time,
providing
a
modular
strategy
synthesis
stereospecific
diboryl‐functionalized
cyclopropanes.
chiral
gem
‐diborylcyclopropanes
are
synthesized
excellent
enantioselectivity
aid
auxiliary.
Based
on
powerful
transformable
ability
boryl
group,
those
challenging
multi‐quaternary
carbon
centers
in
cyclopropane
units
have
been
facilely
constructed
stereoselectivity.
Control
experiments
indicate
that
groups
necessary
both
chemoselectivity
and
stereoselectivity
control.
Язык: Английский
Organocatalytic Asymmetric Allylic Benzylborylation via Fluoride-Assisted Catalytic Generation of α-Boryl Carbanionic Intermediates
Organic Letters,
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 20, 2024
Herein
we
describe
the
organocatalytic
asymmetric
allylic
benzylborylation
of
allyl
fluorides
with
α-silyl
benzylboronic
esters.
The
catalytic
protocol
leverages
singular
features
fluoride
as
an
unconventional
leaving
group,
enabling
generation
reactive
α-boryl
carbanion
species
through
desilylative
activation.
It
allows
construction
a
wide
set
homoallylic
benzylated
organoboronates
bearing
two
contiguous
stereocenters.
chiral
boronate
installed
in
products
serves
synthetic
lynchpin
to
construct
complex
chemical
architectures
stereospecific
manner.
Язык: Английский
Palladium‐Catalyzed Cascade Heck Coupling and Allylboration of Iododiboron Compounds via Diboryl Radicals
Angewandte Chemie,
Год журнала:
2024,
Номер
136(18)
Опубликована: Март 6, 2024
Abstract
Geminal
bis(boronates)
are
versatile
synthetic
building
blocks
in
organic
chemistry.
The
fact
that
they
predominantly
serve
as
nucleophiles
the
previous
reports,
however,
has
restrained
their
potential.
Herein
we
disclose
ambiphilic
reactivity
of
α‐halogenated
geminal
bis(boronates),
which
first
catalytic
utilization
was
accomplished
by
merging
a
formal
Heck
cross‐coupling
with
highly
diastereoselective
allylboration
aldehydes
or
imines,
providing
new
avenue
for
rapid
assembly
polyfunctionalized
boron‐containing
compounds.
We
demonstrated
this
cascade
reaction
is
efficient
and
compatible
various
functional
groups,
wide
range
heterocycles.
In
contrast
to
classical
Pd(0/II)
scenario,
mechanistic
experiments
DFT
calculations
have
provided
strong
evidence
cycle
involving
Pd(I)/diboryl
carbon
radical
intermediates.
Язык: Английский