Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
121(8), P. 4373 - 4505
Published: March 19, 2021
This
Review
compiles
the
evolution,
mechanistic
understanding,
and
more
recent
advances
in
enantioselective
Pd-catalyzed
allylic
substitution
decarboxylative
oxidative
substitutions.
For
each
reaction,
catalytic
data,
as
well
examples
of
their
application
to
synthesis
complex
molecules,
are
collected.
Sections
which
we
discuss
key
aspects
for
high
selectivity
a
comparison
with
other
metals
(with
advantages
disadvantages)
also
included.
asymmetric
substitution,
data
grouped
according
type
nucleophile
employed.
Because
prominent
position
use
stabilized
carbon
nucleophiles
heteronucleophiles,
many
chiral
ligands
have
been
developed.
To
better
compare
results,
they
presented
by
ligand
types.
reactions
mainly
promoted
PHOX
or
Trost
ligands,
justifies
organizing
this
section
chronological
order.
results
used.
Journal of the American Chemical Society,
Journal Year:
2020,
Volume and Issue:
142(31), P. 13515 - 13522
Published: June 29, 2020
Alkene
dicarbofunctionalizations
enable
the
streamlined
construction
of
aliphatic
structures
and
have
thus
been
subject
intense
research
efforts.
Despite
significant
progress,
catalytic
asymmetric
variants
remain
scarce.
Inspired
by
advantages
reductive
cross-coupling
approaches,
we
present
here
a
highly
efficient
intermolecular
Ni-catalyzed
dicarbofunctionalization
alkenes.
Two
distinct
readily
available
electrophiles,
namely,
Csp2-
Csp3-halides,
are
added
simultaneously
across
variety
olefins
(vinyl
amides,
vinyl
boranes,
phosphonates)
at
room
temperature
in
regio-
enantioselective
manner.
The
reaction,
devoid
sensitive
organometallic
reagents,
takes
advantage
an
situ
generated
chiral
alkyl
Ni(III)-intermediate
to
ensure
stereodefined
outcome
Csp3–Csp2
bond-forming
reaction.
An
(l)-(+)-isoleucine
bisoxazoline
ligand
presence
coordinating
sites
on
alkene
key
for
successful
these
"asymmetric
radical
relayed
couplings"
(ARRRCs).
Further,
multiple
transformations
amides
obtained
this
process
showcase
potential
new
methodology
straightforward
assembly
building
blocks
such
as
primary
secondary
amines
oxazolines,
highlighting
its
synthetic
utility.
Organic & Biomolecular Chemistry,
Journal Year:
2018,
Volume and Issue:
16(7), P. 1050 - 1064
Published: Jan. 1, 2018
Recently,gem-diborylalkanes
have
attracted
much
attention
as
versatile
building
blocks
and
fundamental
intermediates
in
organic
synthesis,
because
they
enable
multiple
C–C
bond
construction
further
transformation
at
C–B
bonds.
Angewandte Chemie International Edition,
Journal Year:
2018,
Volume and Issue:
57(24), P. 7196 - 7199
Published: April 27, 2018
Abstract
The
first
catalytic
enantioselective
γ‐boryl
substitution
of
CF
3
‐substituted
alkenes
is
reported.
A
series
was
treated
with
a
diboron
reagent
in
the
presence
copper(I)/Josiphos
catalyst
to
afford
corresponding
optically
active
γ,γ‐
gem
‐difluoroallylboronates
high
enantioselectivity.
thus
obtained
products
could
be
readily
converted
into
difluoromethylene‐containing
homoallylic
alcohols
using
highly
stereospecific
allylation
reactions.
Organic Letters,
Journal Year:
2018,
Volume and Issue:
20(2), P. 357 - 360
Published: Jan. 5, 2018
The
efficient
Pd-catalyzed
Heck
reaction
of
diverse
tertiary
alkyl
halides
with
alkenes
has
been
developed.
Unactivated
efficiently
react
at
room
temperature
under
visible
light
irradiation
no
exogenous
photosensitizers
required.
For
activated
halides,
the
same
catalytic
system
works
well
without
light.
These
methods
offer
a
general
access
to
electronically
possessing
quaternary
and
functionalized
allylic
carbon
centers.
substituents
these
centers
include
alkyl-,
carbalkoxy-,
tosyl-,
phosphonyl-,
boronate
groups.
It
was
also
shown
that
end-game
mechanism
this
transformation
may
vary
depending
on
type
substrates
used.
Journal of the American Chemical Society,
Journal Year:
2018,
Volume and Issue:
140(48), P. 16387 - 16391
Published: Nov. 2, 2018
Unprecedented
hydroxy-alkynylation
and
-alkenylation
reactions
of
arylalkenes
have
been
developed
through
electrochemically
enabled
addition
an
organotrifluoroborate
reagent
H2O
across
the
double
bond
alkene.
The
use
electrochemistry
to
promote
these
oxidative
alkene
1,2-difunctionalization
not
only
obviates
need
for
transition-metal
catalysts
oxidizing
reagents
but
also
ensures
high
regio-
chemoselectivity
afford
homopropargylic
or
homoallylic
alcohols.
possibility
extending
electrochemical
difunctionalization
strategy
other
carbo-heterofunctionalization
has
demonstrated.
NPG Asia Materials,
Journal Year:
2018,
Volume and Issue:
10(4), P. 90 - 106
Published: April 1, 2018
Nanoarchitectonics
is
a
new
paradigm
to
combine
and
unify
nanotechnology
with
other
sciences
technologies,
such
as
supramolecular
chemistry,
self-assembly,
self-organization,
materials
technology
for
manipulation
of
the
size
material
objects,
even
biotechnology
hybridization
bio-components.
The
nanoarchitectonic
concept
leads
synergistic
combination
various
methodologies
in
production,
including
atomic/molecular-level
control,
field-controlled
organization.
focus
this
review
on
soft
2D
nanoarchitectonics.
Scientific
views
nanomaterials
are
not
fully
established
compared
those
rigid
materials.
Here,
we
collect
recent
examples
constructions
functional
systems
components.
These
selected
according
following
three
categories
basis
spatial
density
motional
freedom:
(i)
well-packed
oriented
organic
rational
design
component
molecules
device
applications,
(ii)
well-defined
assemblies
porous
structures
network
materials,
(iii)
control
molecular
machines
receptors
certain
freedom
confined
two
dimensions.
pursuit
ever
smaller
has
required
be
combined
fields
or
biomolecules—these
approaches
now
unified
‘nanoarchitectonics’.
A
Japan-based
team
led
by
Katsuhiko
Ariga
at
National
Institute
Materials
Science
Tsukuba
developments
traditionally
less
explored
than
graphene.
Sheets
composed
held
together
weak
forces,
typically
hydrogen
bonding
metal
coordination,
have
been
constructed
that
serve
crystalline
semiconductors,
machines,
receptors.
film
living
cells
also
obtained
liquid–liquid
interface.
achievements
show
nanoarchitectonics
holds
great
promise
variety
ranging
from
electronics
biomaterials.
target
because
scientific
presented
freedoms:
controls
nature
plain.
Journal of the American Chemical Society,
Journal Year:
2020,
Volume and Issue:
142(50), P. 20979 - 20986
Published: Dec. 1, 2020
A
user-friendly
approach
is
presented
to
sidestep
the
venerable
Grignard
addition
unactivated
ketones
access
tertiary
alcohols
by
reversing
polarity
of
disconnection.
In
this
work
a
ketone
instead
acts
as
nucleophile
when
adding
simple
olefins
accomplish
same
overall
transformation.
The
scope
coupling
broad
enabled
using
an
electrochemical
approach,
and
reaction
scalable,
chemoselective,
requires
no
precaution
exclude
air
or
water.
Multiple
applications
demonstrate
simplifying
nature
on
multistep
synthesis,
mechanistic
studies
point
intuitive
mechanism
reminiscent
other
chemical
reductants
such
SmI2
(which
cannot
reaction).
Journal of the American Chemical Society,
Journal Year:
2017,
Volume and Issue:
139(14), P. 5027 - 5030
Published: March 25, 2017
Palladium-catalyzed
conjunctive
cross-coupling
is
used
for
the
synthesis
of
enantioenriched
allylboron
reagents.
This
reaction
employs
nonsymmetric
bis(alkenyl)borates
as
substrates
and
appears
to
occur
by
a
mechanism
that
involves
selective
activation
less
substituted
alkene
followed
migration
more
during
course
Pd-induced
metalate
rearrangement.
