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
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
Chemistry - A European Journal,
Год журнала:
2021,
Номер
27(62), С. 15277 - 15326
Опубликована: Сен. 9, 2021
Abstract
This
review
discusses
recent
advances
in
the
chemistry
of
saturated
boronic
acids,
boronates,
and
trifluoroborates.
Applications
title
compounds
design
boron‐containing
drugs
are
surveyed,
with
special
emphasis
on
α‐amino
derivatives.
A
general
overview
as
modern
tools
to
construct
C(sp
3
)−C
)‐heteroatom
bonds
is
given,
including
developments
Suzuki‐Miyaura
Chan‐Lam
cross‐couplings,
single‐electron‐transfer
processes
metallo‐
organocatalytic
photoredox
reactions,
transformations
boron
“ate”
complexes.
Finally,
an
attempt
summarize
current
state
art
synthesis
trifluoroborates
made,
a
brief
mention
“classical”
methods
(transmetallation
organolithium/magnesium
reagents
species,
anti‐Markovnikov
hydroboration
alkenes,
modification
alkenyl
compounds)
focus
methodologies
(boronation
alkyl
(pseudo)halides,
derivatives
carboxylic
alcohols,
primary
amines,
boronative
C−H
activation,
novel
approaches
alkene
hydroboration,
1,2‐metallate‐type
rearrangements).
Journal of the American Chemical Society,
Год журнала:
2021,
Номер
143(13), С. 4921 - 4927
Опубликована: Март 23, 2021
Alkenyl
boronates
add
to
Ir(π-allyl)
intermediates
with
high
enantioselectivity.
A
1,2-metalate
shift
forms
a
second
C–C
bond
and
sets
1,3-stereochemical
relationship.
The
three-component
coupling
provides
tertiary
boronic
esters
that
can
undergo
multiple
additional
functionalizations.
An
extension
trisubstituted
olefins
three
contiguous
stereocenters.
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:
2023,
Номер
62(32)
Опубликована: Июнь 15, 2023
Abstract
Asymmetric
cross‐couplings
based
on
1,2‐carbon
migration
from
B‐ate
complexes
have
been
developed
efficiently
to
access
valuable
organoboronates.
However,
enantioselective
reactions
triggered
by
1,2‐boron
shift
remained
be
unaddressed
synthetic
challenge.
Here,
Ir‐catalyzed
asymmetric
allylic
alkylation
enabled
was
developed.
In
this
reaction,
we
disclosed
that
excellent
enantioselectivities
were
achieved
through
an
interesting
dynamic
kinetic
resolution
(DKR)
process
of
carbonates
at
the
elevated
temperature.
Notably,
highly
(bis‐boryl)alkenes
array
diversifications
versatile
molecules.
Extensive
experimental
and
computational
studies
conducted
elucidate
reaction
mechanism
DKR
clarify
origin
enantioselectivities.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(23), С. 15850 - 15859
Опубликована: Май 28, 2024
Light-driven
strategies
that
enable
the
chemoselective
activation
of
a
specific
bond
in
multifunctional
systems
are
comparatively
underexplored
comparison
to
transition-metal-based
technologies,
yet
desirable
when
considering
controlled
exploration
chemical
space.
With
current
drive
discover
next-generation
therapeutics,
reaction
design
enables
strategic
incorporation
an
sp3
carbon
center,
containing
multiple
synthetic
handles
for
subsequent
space
would
be
highly
enabling.
Here,
we
describe
photoactivation
ambiphilic
C1
units
generate
α-bimetalloid
radicals
using
only
Lewis
base
and
light
source
directly
activate
C–I
bond.
Interception
these
transient
with
various
SOMOphiles
rapid
synthesis
organic
scaffolds
(B,
Si,
Ge)
orthogonal
activation.
In-depth
theoretical
mechanistic
studies
reveal
prominent
role
2,6-lutidine
forming
photoactive
charge
transfer
complex
stabilizing
situ
generated
iodine
radicals,
as
well
influential
boron
p-orbital
activation/weakening
This
simple
efficient
methodology
enabled
expedient
access
functionalized
3D
frameworks
can
further
derivatized
available
technologies
C–B
C–Si
Organic Letters,
Год журнала:
2022,
Номер
24(4), С. 1100 - 1104
Опубликована: Янв. 26, 2022
Radical
1,3-carboheteroarylation
and
1,3-hydroalkylation
of
allylboronic
esters
comprising
a
1,2-boron
shift
is
reported.
Allylboronic
are
generally
used
in
synthesis
as
allylation
reagents,
where
the
boronic
ester
moiety
gets
lost.
In
introduced
cascades,
alkylboronic
obtained
with
boron
entity
remaining
product.
The
carboheteroarylation
conducted
without
metal
catalyst,
achieved
using
iron
catalysis.
Both
reactions
work
efficiently
under
mild
conditions.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(34)
Опубликована: Июнь 16, 2023
Abstract
Operationally
simple
strategies
to
assemble
boron
containing
organic
frameworks
are
highly
enabling
in
synthesis.
While
conventional
retrosynthetic
logic
has
engendered
many
platforms
focusing
on
the
direct
formation
of
C−B
bonds,
α‐boryl
radicals
have
recently
reemerged
as
versatile
open‐shell
alternatives
access
organoborons
via
adjacent
C−C
bond
formation.
Direct
light‐enabled
α‐activation
is
currently
contingent
photo‐
or
transition
metal‐catalysis
activation
efficiently
generate
radical
species.
Here,
we
disclose
a
facile
α‐halo
boronic
esters
using
only
visible
light
and
Lewis
base
enable
homolytic
scission.
Intermolecular
addition
styrenes
facilitates
rapid
construction
E
‐allylic
esters.
The
simplicity
permits
strategic
merger
this
construct
with
selective
energy
transfer
catalysis
complimentary
stereodivergent
synthesis
Z
