Angewandte Chemie,
Год журнала:
2020,
Номер
132(39), С. 17005 - 17018
Опубликована: Июнь 27, 2020
Abstract
The
stereospecific
1,2‐migration
of
boronate
complexes
is
one
the
most
representative
reactions
in
boron
chemistry.
This
process
has
been
used
extensively
to
develop
powerful
methods
for
asymmetric
synthesis,
with
applications
spanning
from
pharmaceuticals
natural
products.
Typically,
driven
by
displacement
an
α‐leaving
group,
oxidation
α‐boryl
radical,
or
electrophilic
activation
alkenyl
complex.
aim
this
article
summarize
recent
advances
rapidly
expanding
field
electrophile‐induced
groups
sp
2
and
3
carbon
centers.
It
will
be
shown
that
three
different
conceptual
approaches
can
utilized
enable
complexes:
Zweifel‐type
reactions,
catalytic
conjunctive
coupling
transition
metal‐free
–sp
couplings.
A
discussion
reaction
scope,
mechanistic
insights,
synthetic
work
described
also
presented.
Angewandte Chemie International Edition,
Год журнала:
2020,
Номер
59(39), С. 16859 - 16872
Опубликована: Июнь 27, 2020
The
stereospecific
1,2-migration
of
boronate
complexes
is
one
the
most
representative
reactions
in
boron
chemistry.
This
process
has
been
used
extensively
to
develop
powerful
methods
for
asymmetric
synthesis,
with
applications
spanning
from
pharmaceuticals
natural
products.
Typically,
driven
by
displacement
an
α-leaving
group,
oxidation
α-boryl
radical,
or
electrophilic
activation
alkenyl
complex.
aim
this
article
summarize
recent
advances
rapidly
expanding
field
electrophile-induced
groups
sp
Chemical Communications,
Год журнала:
2019,
Номер
56(1), С. 13 - 25
Опубликована: Ноя. 27, 2019
Organoborons
are
extremely
important
for
synthetic
organic
chemistry;
they
can
serve
as
advanced
intermediates
a
variety
of
transformations.
Such
well-known
transformation
involves
the
loss
boron
moiety,
creating
alkyl
radicals.
Although
these
originally
developed
protocols
radical
generation
remain
in
active
use
today,
recent
years
their
α-boryl
carbon-centred
radicals
have
been
joined
by
new
array
strategies
that
offer
unique
reactivity
to
forge
wider
diversity
organoborons
often
operate
under
mild
and
benign
conditions.
Herein,
we
will
highlight
stability
α-borylalkyl
remarkably
advances
order
further
utilise
them
C-C
C-heteroatom
bond
formation.
Their
this
purpose
has
reported
over
last
decade
an
attempt
guide
community.
Various
transition-metal
metal-free
methods
presented,
more
photoredox
approaches
discussed,
mainly
period
2009-2019.
Journal of the American Chemical Society,
Год журнала:
2020,
Номер
143(1), С. 471 - 480
Опубликована: Дек. 21, 2020
Alkyl
boronic
acids
and
esters
play
an
important
role
in
the
synthesis
of
C(sp3)-rich
medicines,
agrochemicals,
material
chemistry.
This
work
describes
a
new
type
transition-metal-free
mediated
transformation
to
enable
construction
sterically
hindered
alkyl
boron
reagents
practical
modular
manner.
The
broad
generality
functional
group
tolerance
this
method
is
extensively
examined
through
variety
substrates,
including
late-stage
functionalization
scaffolds
relevant
medicinal
strategic
significance
approach,
with
as
linchpins,
demonstrated
various
downstream
functionalizations
compounds.
two-step
concurrent
cross-coupling
resembling
formal
flexible
alkyl-alkyl
couplings,
provides
general
entry
synthetically
challenging
high
Fsp3-containing
drug-like
scaffolds.
Advanced Synthesis & Catalysis,
Год журнала:
2019,
Номер
362(11), С. 2077 - 2087
Опубликована: Дек. 24, 2019
Abstract
1,2‐Boron
ate
rearrangements
represent
a
fundamental
class
of
transformations
to
establish
new
C−C
bonds
while
retaining
the
valuable
boron
moiety
in
product.
In
established
ionic
processes,
complex
is
activated
by
an
external
electrophile
induce
1,2‐migration
from
adjacent
sp
3
or
2
carbon
atom.
Recently,
two
complementary
radical
polar
crossover
approaches
have
been
explored
for
both
classes,
1,2‐migrations
and
centers.
This
review
describes
general
concepts
this
emerging
research
field
summarizes
recent
developments
radical‐induced
carbon.
magnified
image
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(38)
Опубликована: Июнь 24, 2022
Recently
the
fruitful
merger
of
organoboron
chemistry
and
photocatalysis
has
come
to
forefront
organic
synthesis,
resulting
in
development
new
technologies
access
complex
(non)borylated
frameworks.
Central
success
this
combination
is
control
boron
hybridisation.
Contingent
on
photoactivation
mode,
as
its
neutral
planar
form
or
tetrahedral
boronate
can
be
used
regulate
reactivity.
This
Minireview
highlights
current
state
art
photocatalytic
processes
utilising
compounds,
paying
particular
attention
role
hybridisation
for
target
transformation.
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.
Organic Letters,
Год журнала:
2020,
Номер
22(19), С. 7450 - 7454
Опубликована: Сен. 24, 2020
Herein
we
disclose
a
metal-free,
N/O-centered
radical-promoted
Minisci
reaction,
in
which
the
coupling
of
various
heteroarenes
with
simple
alkanes
proceeds
under
mild
conditions.
The
reaction
conditions
are
neutral;
no
extra
acid
is
added
to
preactivate
N-heteroarenes
reaction.
N-/O-centered
radicals
generated
directly
from
amide
(TsNHMe)
or
alcohol
(CF3CH2OH)
visible-light
irradiation.
This
green
and
eco-friendly
synthetic
process
may
find
potential
use
medicinal
chemistry.
