Angewandte Chemie International Edition,
Journal Year:
2019,
Volume and Issue:
58(14), P. 4612 - 4616
Published: Feb. 11, 2019
Abstract
An
unprecedented
arylboration
of
unactivated
terminal
alkenes,
featuring
1,
n
‐regioselectivity,
has
been
achieved
by
nickel
catalysis.
The
nitrogen‐based
ligand
plays
an
essential
role
in
the
success
this
three‐component
reaction.
This
transformation
displays
good
regioselectivity
and
excellent
functional‐group
tolerance.
In
addition,
incorporation
a
boron
group
into
products
provides
substantial
opportunities
for
further
transformations.
Also
demonstrated
is
that
can
be
readily
transformed
pharmaceutically
relevant
molecules.
Unexpectedly,
preliminary
mechanistic
studies
indicate
although
metal
migration
favors
α‐position
boron,
selective
decisive
bond
formation
favored
at
benzylic
position.
Chemical Society Reviews,
Journal Year:
2020,
Volume and Issue:
49(7), P. 2060 - 2118
Published: Jan. 1, 2020
This
review
article
provides
an
overview
of
progress
in
asymmetric
synthesis
allylic
compoundsviahydrofunctionalisation
and
difunctionalisation
dienes,
allenes,
alkynes.
Journal of the American Chemical Society,
Journal Year:
2018,
Volume and Issue:
140(6), P. 2080 - 2084
Published: Jan. 30, 2018
We
describe
a
fully
stereodivergent
synthesis
of
range
α,α-disubstituted
α-amino
acids
via
an
Ir/Cu-catalyzed
α-allylation
readily
available
imine
esters.
The
introduction
Cu-Phox
complex-activated
ester
into
the
chiral
iridium-catalyzed
allylic
allylation
process
is
crucial
for
its
high
reactivity
and
excellent
enantio-
diastereoselectivity
(up
to
>99%
ee
>20:1
dr).
Importantly,
two
catalysts
allow
full
control
over
configuration
stereocenters,
affording
all
stereoisomers
desired
products.
utility
this
methodology
was
demonstrated
by
synthesizing
dipeptides
analogues
bioactive
molecules
in
manner.
Chemical Reviews,
Journal Year:
2020,
Volume and Issue:
120(24), P. 13382 - 13433
Published: Nov. 29, 2020
Synergistic
catalysis,
a
type
of
plural
catalysis
which
utilizes
at
least
two
different
catalysts
to
enable
reaction
between
separately
activated
substrates,
has
unlocked
plethora
previously
unattainable
transformations
and
novel
chemical
reactivity.
Despite
the
appreciable
utility
synergistic
specific
examples
involving
transition
metals
have
been
limited,
as
ensuring
judicious
choice
parameters
prevent
deactivation
catalysts,
undesirable
monocatalytic
event(s)
leading
side
products,
or
premature
termination
other
potentially
troublesome
outcomes
present
formidable
challenge.
Excluding
those
driven
by
photocatalytic
mechanisms,
this
review
will
highlight
reported
reactions
that
make
use
simultaneous
catalytic
cycles
metal
catalysts.
Journal of the American Chemical Society,
Journal Year:
2018,
Volume and Issue:
140(4), P. 1239 - 1242
Published: Jan. 10, 2018
We
report
stereodivergent
allylic
substitution
reactions
of
esters
with
prochiral
enolates
derived
from
azaaryl
acetamides
and
acetates
to
form
products
addition
the
at
most
substituted
carbon
an
allyl
moiety
two
catalysts,
a
chiral
metallacyclic
iridium
complex
bisphosphine-ligated
copper(I)
complex,
which
individually
control
configuration
electrophilic
nucleophilic
atoms,
respectively.
By
simple
permutations
enantiomers
all
four
stereoisomers
containing
stereogenic
centers
were
synthesized
high
diastereoselectivity
enantioselectivity.
A
variety
bearing
pyridyl,
benzothiazolyl,
benzoxazolyl,
pyrazinyl,
quinolinyl
isoquinolinyl
moieties
found
be
suitable
for
this
transformation.
Journal of the American Chemical Society,
Journal Year:
2018,
Volume and Issue:
140(38), P. 12056 - 12068
Published: Aug. 28, 2018
Cobalt/nickel-dual
catalyzed
hydroarylation
of
terminal
olefins
with
iodoarenes
builds
complexity
from
readily
available
starting
materials,
a
high
preference
for
the
Markovnikov
(branched)
product.
Here,
we
advance
mechanistic
model
this
reaction
through
use
progress
kinetic
analysis
(RPKA),
radical
clock
experiments,
and
stoichiometric
studies.
Through
exclusion
competing
hypotheses,
conclude
that
proceeds
an
unprecedented
alkylcobalt
to
nickel
direct
transmetalation.
Demonstration
catalytic
alkene
prefunctionalization,
via
spectroscopic
observation
organocobalt
species,
distinguishes
Csp2–Csp3
cross-coupling
method
conventional
transmetalation
process,
which
employs
organometallic
nucleophile,
bimetallic
oxidative
addition
organohalide
across
nickel,
described
by
scission
subsequent
alkyl
capture
at
second
center.
A
refined
understanding
leads
optimized
procedure
excludes
exogenous
oxidant,
demonstrating
is
net
redox
neutral.
Catalytic
prefunctionalization
cobalt
engagement
cycles
provides
new
platform
merge
these
two
rich
areas
chemistry
in
preparatively
useful
ways.
Journal of the American Chemical Society,
Journal Year:
2017,
Volume and Issue:
139(47), P. 17011 - 17014
Published: Nov. 10, 2017
Herein,
we
report
a
highly
regio-
and
enantioselective
copper-catalyzed
reductive
hydroxymethylation
of
styrenes
1,3-dienes
with
1
atm
CO2.
Diverse
important
chiral
homobenzylic
alcohols
were
readily
prepared
from
styrenes.
Moreover,
variety
also
converted
to
homoallylic
high
yields
excellent
regio-,
enantio-,
Z/E-selectivities.
The
utility
this
transformation
was
demonstrated
by
broad
range
1,3-dienes,
facile
product
modification,
synthesis
bioactive
compounds
(R)-(−)-curcumene
(S)-(+)-ibuprofen.
Mechanistic
studies
the
carboxylation
phenylethylcopper
complexes
CO2
as
one
key
step.
Chemical Society Reviews,
Journal Year:
2020,
Volume and Issue:
49(22), P. 8036 - 8064
Published: Jan. 1, 2020
Transition
metal-catalysed
cross-coupling
reactions
are
widely
used
for
construction
of
carbon-carbon
and
carbon-heteroatom
bonds.
However,
compared
to
aryl
or
alkenyl
electrophiles,
the
unactivated
alkyl
electrophiles
containing
β
hydrogens
remains
a
challenge.
Over
past
few
years,
use
suitable
ligands
such
as
bulky
phosphines
N-heterocyclic
carbenes
(NHCs)
has
enabled
not
only
limited
traditional
with
Grignard
reagents,
but
also
including
diverse
range
organic
transformations
via
either
SN2
radical
pathways.
This
review
provides
comprehensive
overview
recent
development
in
copper-catalysed
C-C,
C-N,
C-B,
C-Si
C-F
bond-forming
using
electrophiles.
Journal of the American Chemical Society,
Journal Year:
2020,
Volume and Issue:
142(18), P. 8097 - 8103
Published: April 19, 2020
A
stereodivergent
Pd/Cu
catalyst
system
has
been
developed
for
the
unprecedented
dynamic
kinetic
asymmetric
transformation
(DyKAT)
of
racemic
unsymmetrical
1,3-disubstituted
allylic
acetates
with
prochiral
aldimine
esters.
series
α,α-disubstituted
α-amino
acids
bearing
vicinal
stereocenters
were
easily
prepared
excellent
enantioselectivities
(up
to
>99%
ee)
and
diastereoselectivities
>20:1
dr).
Moreover,
all
four
stereoisomers
product
can
be
readily
obtained
simply
by
switching
configurations
two
chiral
metal
catalysts.
Furthermore,
present
work
highlights
power
synergistic
catalysis
consisting
common
bidentate
ligands
synthesis.
