Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(29), P. 20357 - 20369
Published: June 13, 2024
Developing
a
general,
highly
efficient,
and
enantioselective
catalytic
method
for
the
synthesis
of
chiral
alcohols
is
still
formidable
challenge.
We
report
in
this
article
asymmetric
transfer
hydrogenation
(ATH)
N-methyliminodiacetyl
(MIDA)
acylboronates
as
general
substrate-independent
entry
to
enantioenriched
secondary
alcohols.
ATH
acyl-MIDA-boronates
with
(het)aryl,
alkyl,
alkynyl,
alkenyl,
carbonyl
substituents
delivers
variety
α-boryl
The
latter
are
used
range
stereospecific
transformations
based
on
boron
moiety,
enabling
carbinols
two
closely
related
α-substituents,
which
cannot
be
obtained
high
enantioselectivities
using
direct
methods,
such
(R)-cloperastine
intermediate.
Computational
studies
illustrate
that
BMIDA
group
privileged
enantioselectivity-directing
Noyori–Ikariya
compared
conventionally
aryl
alkynyl
groups
due
favorable
CH–O
attractive
electrostatic
interaction
between
η6-arene-CH
catalyst
σ-bonded
oxygen
atoms
BMIDA.
work
expands
domain
conventional
shows
its
huge
potential
addressing
challenges
symmetric
synthesis.
Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
121(21), P. 13238 - 13341
Published: Oct. 7, 2021
Organoboron
reagents
represent
a
unique
class
of
compounds
because
their
utility
in
modern
synthetic
organic
chemistry,
often
affording
unprecedented
reactivity.
The
transformation
the
carbon–boron
bond
into
carbon–X
(X
=
C,
N,
and
O)
stereocontrolled
fashion
has
become
invaluable
medicinal
agrochemistry,
natural
products
chemistry
as
well
materials
science.
Over
past
decade,
first-row
d-block
transition
metals
have
increasingly
widely
used
catalysts
for
formation
bond,
traditionally
catalyzed
by
expensive
precious
metals.
This
recent
focus
on
alternative
enabled
growth
fundamental
methods
organoboron
chemistry.
review
surveys
current
state-of-the-art
use
element-based
bonds.
Accounts of Chemical Research,
Journal Year:
2023,
Volume and Issue:
56(22), P. 3246 - 3259
Published: Nov. 1, 2023
ConspectusChain-walking
offers
extensive
opportunities
for
innovating
synthetic
methods
that
involve
constructing
chemical
bonds
at
unconventional
sites.
This
approach
provides
previously
inaccessible
retrosynthetic
disconnections
in
organic
synthesis.
Through
chain-walking,
transition
metal-catalyzed
alkene
difunctionalization
reactions
can
take
place
a
1,n-addition
(n
≠
2)
mode.
Unlike
classical
1,2-regioselective
reactions,
there
remains
scarcity
of
reports
regarding
migratory
patterns.
Moreover,
the
range
olefins
utilized
these
studies
is
quite
limited.About
five
years
ago,
our
research
group
embarked
on
project
aimed
developing
valuable
alkenes
through
chain-walking.
Our
focus
was
carboboration
utilizing
nickel
catalysis.
The
reaction
commences
with
insertion
an
olefin
into
Ni-Bpin
species.
Subsequently,
thermodynamically
stable
alkyl
complex
generated
chain-walking
process.
then
couples
carbon-based
electrophile,
leading
to
formation
alkylboron
compound.
It
worth
highlighting
success
transformations
relies
significantly
utilization
bisnitrogen-based
ligand
and
LiOMe
as
B2pin2
activator.
Synthetically,
establish
robust
platform
rapid
efficient
synthesis
wide
structurally
diverse
organoboron
compounds,
which
are
not
facially
accessed
by
conventional
methods.
incorporation
versatile
boron
introduces
wealth
possibilities
subsequent
diversifications,
enhancing
value
resulting
products
allowing
creation
broader
derivatives
applications.This
Account
comprehensive
overview
efforts
advancements
field
unactivated
using
We
begin
outlining
development
series
1,1-regioselective
terminal
alkenes.
A
significant
placed
initial
integration
boronate,
only
triggers
metal
species
but
also
exerts
control
over
remote
stereochemistry
involving
substituted
methylenecyclohexenes.
Continuing
exploration,
remarkable
achieved
1,3-regio-
cis-stereoselectivity
when
dealing
cyclic
Remarkably,
catalysis
enables
heterocyclic
be
viable
coupling
partners
within
transformations.
it
grants
us
ability
achieve
regioselectivity
cyclohexenes
unattainable,
thus
expanding
horizons
regiochemical
reactions.
Lastly,
we
present
evolution
ligand-modulated
regiodivergent
allylarenes.
By
gaining
insights
underlying
mechanisms
driving
regiodivergence,
lay
strong
foundation
tackling
challenges
related
selecting
specific
sites
especially
multiple
factors.
anticipate
findings,
coupled
mechanistic
we've
gained,
will
advance
realm
contribute
understanding
selectivity
this
nature.
advancement
catalyze
intricate
functional
molecules,
contributing
compounds
chemistry.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(38)
Published: June 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.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(26), P. 11546 - 11552
Published: June 23, 2022
Copper-catalyzed
stereospecific
cross-couplings
of
boronic
esters
are
reported.
Boron
"ate"
complexes
derived
from
pinacol
and
tert-butyl
lithium
undergo
transmetalation
to
copper
cyanide,
followed
by
coupling
with
alkynyl
bromides,
allyl
halides,
propargylic
β-haloenones,
hydroxylamine
esters,
acyl
chlorides.
Through
this
simple
transformation,
commercially
available
inexpensive
compounds
can
be
employed
convert
primary
secondary
alkylboronic
a
wide
array
synthetically
useful
compounds.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(13), P. 7638 - 7647
Published: March 22, 2023
The
efficient
and
selective
functionalization
of
icosahedral
carboranes
(C2B10H12)
at
the
boron
vertexes
is
a
long-standing
challenge
owing
to
presence
10
inert
B-H
bonds
in
similar
chemical
environment.
Herein,
we
report
new
reaction
paradigm
for
direct
via
homolysis
enabled
by
nitrogen-centered
radical-mediated
hydrogen
atom
transfer
(HAT)
strategy.
Both
HAT
process
carborane
bond
resulting
boron-centered
carboranyl
radical
intermediate
have
been
confirmed
experimentally.
occurs
most
electron-rich
vertex
with
lowest
dissociation
energy
(BDE).
Using
this
strategy,
diverse
derivatization,
including
thiolation,
selenation,
alkynylation,
alkenylation,
cyanation,
halogenation,
achieved
satisfactory
yields
under
photoinitiated
condition
metal-free
redox-neutral
fashion.
Moreover,
synthetic
utility
current
protocol
was
also
demonstrated
both
scale-up
construction
carborane-based
functional
molecules.
Therefore,
methodology
opens
pathway
functionalization,
which
distinct
from
heterolytic
mechanism
traditional
strategies.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(25), P. 13603 - 13614
Published: June 6, 2023
Chiral
boronic
esters
are
a
class
of
versatile
building
blocks.
We
describe
herein
an
asymmetric
nickel-catalyzed
borylative
coupling
terminal
alkenes
with
nonactivated
alkyl
halides.
The
success
this
reaction
is
ascribed
to
the
application
chiral
anionic
bisoxazoline
ligand.
This
study
provides
three-component
strategy
access
α-
and
β-stereogenic
from
easily
accessible
starting
materials.
protocol
characterized
by
mild
conditions,
wide
substrate
scope
high
regio-
enantioselectivity.
also
showcase
value
method
in
simplifying
synthesis
several
drug
molecules.
Mechanistic
studies
suggest
that
generation
enantioenriched
bearing
α-stereogenic
center
results
stereoconvergent
process,
while
enantioselectivity-controlling
step
β-stereocenter
switched
olefin
migratory
insertion
due
coordination
ester
group.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(11), P. 7791 - 7802
Published: March 10, 2024
The
development
of
new
synthetic
methods
for
B–H
bond
activation
has
been
an
important
research
area
in
boron
cluster
chemistry,
which
may
provide
opportunities
to
broaden
the
application
scope
clusters.
Herein,
we
present
a
reaction
strategy
direct
site-selective
functionalization
nido-carboranes
initiated
by
photoinduced
cage
via
noncovalent
cage···π
interaction.
As
result,
nido-carborane
radical
is
generated
through
single
electron
transfer
from
3D
2D
photocatalyst
upon
irradiation
with
green
light.
resulting
transient
could
be
directly
probed
advanced
time-resolved
EPR
technique.
In
air,
subsequent
transformations
active
have
led
efficient
and
selective
B–N,
B–S,
B–Se
couplings
presence
N-heterocycles,
imines,
thioethers,
thioamides,
selenium
ethers.
This
protocol
also
facilitates
both
late-stage
modification
drugs
synthesis
nido-carborane-based
drug
candidates
neutron
capture
therapy
(BNCT).
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(15), P. 11318 - 11331
Published: July 15, 2024
Catalytic
enantioselective
borylation
reactions
of
unsaturated
bonds
as
powerful
tools
for
the
synthesis
diverse
chiral
organoboron
compounds
have
gained
much
attention
and
wide
applications
in
various
fields.
However,
atroposelective
arylboration
reaction
with
carbon–carbon
triple
1,3-enynes
to
obtain
axially
1,3-dienylboronates
remains
an
elusive
significant
challenge.
Hence,
we
develop
a
cooperative
copper-
palladium-catalyzed
assemble
plentiful
function
enriched
single
step
from
easily
available
1,3-enynes,
B2pin2,
aryl
bromides
high
levels
chemo-,
regio-,
stereo-,
atroposelectivity.
The
mild
conditions
lead
good
functional
group
tolerance,
which
is
proven
by
broad
substrate
scope
late-stage
functionalizations
bioactive
or
drug
molecules.
Moreover,
can
be
scaled
up,
series
further
transformations
achieved.
It
worth
emphasizing
that
several
olefin
catalysts
ligands
axial
chirality
also
synthesized
through
corresponding
elaborations
such
products,
explains
transformative
ability
application
potential
1,3-dienylboronates.
mechanism
experiment
density
theory
(DFT)
calculations
revealed
process
copper
palladium
catalysis,
indicating
chemoselectivity
regioselectivity
boration
are
determined
enyne
insertion
on
copper,
atroposelectivity
controlled
reductive
elimination
center.
Meanwhile,
calculation
demonstrated
distinct
interactions
between
P═O
C═O
groups
Pd
Bpin
center
key
transition
state
formation
products
varying
configurations
while
employing
identical
configuration
ligands.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(30)
Published: May 24, 2022
A
cobalt-catalyzed
asymmetric
sequential
hydroboration/isomerization/hydroboration
of
2-aryl
vinylcyclopropanes
was
for
the
first
time
reported
preparation
valuable
chiral
1,5-bis(boronates)
in
good
yields
with
excellent
enantioselectivity
via
isomerization/hydroboration
a
trisubstituted
alkene
intermediate.
The
reaction
carried
out
smoothly
and
this
protocol
used
syntheses
(-)-preclamol
gram-scale.
two
primary
C(sp3)
-B
bonds
could
be
distinguished
iterative
Suzuki-Miyaura
cross-coupling
reaction,
delivering
1,2,5-triaryl
alkanes
enantioselectivity.
Based
on
experimental
computational
studies,
cobalt-hydride
species
proposed
as
active
intermediate
hydroboration,
isomerization,
second
hydroboration
reactions.