Angewandte Chemie,
Journal Year:
2019,
Volume and Issue:
131(39), P. 13992 - 13997
Published: July 8, 2019
Abstract
Metal
hydride
catalyzed
hydrocarbonation
reactions
of
alkenes
are
an
efficient
approach
to
construct
new
carbon–carbon
bonds
from
readily
available
alkenes.
However,
the
regioselectivity
remains
challenging
be
controlled.
In
nickel
(NiH)
hydrocarbonation,
linear
selectivity
is
most
often
obtained
because
relative
stability
Ni–alkyl
intermediate
over
its
branched
counterpart.
Herein,
we
show
that
boronic
pinacol
ester
(Bpin)
group
directs
a
Ni‐catalyzed
occur
at
adjacent
carbon
center,
resulting
in
formal
branch
selectivity.
Both
alkyl
and
aryl
halides
can
used
as
electrophiles
this
providing
access
wide
range
secondary
Bpin
derivatives,
which
valuable
building
blocks
synthetic
chemistry.
The
utility
method
demonstrated
by
late‐stage
functionalization
natural
products
drug
molecules,
synthesis
anticancer
agent,
iterative
syntheses.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(16), P. 7189 - 7197
Published: April 18, 2022
A
multi-component
approach
to
structurally
complex
organosulfur
products
is
described
via
the
nickel-catalyzed
1,2-carbosulfenylation
of
unactivated
alkenes
with
organoboron
nucleophiles
and
tailored
electrophiles.
The
key
development
this
transformation
identification
a
modular
N-alkyl-N-(arylsulfenyl)arenesulfonamide
family
sulfur
Tuning
electronic
steric
properties
leaving
group
in
these
reagents
controls
pathway
selectivity,
favoring
three-component
coupling
suppressing
side
reactions,
as
examined
computational
studies.
unique
syn-stereoselectivity
differs
from
traditional
electrophilic
sulfenyl
transfer
processes
involving
thiiranium
ion
intermediate
arises
directed
arylnickel(I)
migratory
insertion
mechanism,
elucidated
through
reaction
kinetics
control
experiments.
Reactivity
regioselectivity
are
facilitated
by
collection
monodentate,
weakly
coordinating
native
directing
groups,
including
sulfonamides,
alcohols,
amines,
amides,
azaheterocycles.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
63(5)
Published: Dec. 15, 2023
The
construction
of
acyclic,
non-adjacent
1,3-stereogenic
centers,
prevalent
motifs
in
drugs
and
bioactive
molecules,
has
been
a
long-standing
synthetic
challenge
due
to
acyclic
nucleophiles
being
distant
from
the
chiral
environment.
In
this
study,
we
successfully
synthesized
highly
valuable
1,2-bis(boronic)
esters
featuring
nonadjacent
1,3-stereocenters.
Notably,
reaction
selectively
produces
migratory
coupling
products
rather
than
alternative
deborylative
allylation
or
direct
byproducts.
This
approach
introduces
new
activation
mode
for
selective
transformations
gem-diborylmethane
asymmetric
catalysis.
Additionally,
found
that
other
gem-diborylalkanes,
previously
challenging
steric
hindrance,
also
participated
reaction.
incorporation
1,2-bis(boryl)alkenes
facilitated
diversification
alkenyl
two
boron
moieties
our
target
compounds,
thereby
enabling
access
broad
array
versatile
molecules.
DFT
calculations
were
performed
elucidate
mechanism
shed
light
on
factors
responsible
observed
excellent
enantioselectivity
diastereoselectivity.
These
determined
arise
ligand-substrate
repulsions
syn-addition
transition
state.
ACS Catalysis,
Journal Year:
2019,
Volume and Issue:
9(8), P. 6896 - 6902
Published: July 2, 2019
An
efficient
and
convenient
pathway
was
developed
for
enantioselective
synthesis
of
chiral
sulfides
by
bifunctional
selenide-catalyzed
electrophilic
azidothiolation
oxythiolation
N-allyl
sulfonamides.
By
this
protocol,
a
variety
vicinal
azidosulfides
oxysulfides
were
obtained
in
good
yields
with
high
enantioselectivities
diastereoselectivities.
In
transformation,
not
only
arylthiolating
reagents
but
also
wide
range
alkylthiolating
worked
very
well.
The
practical
application
method
elucidated
further
transformations
the
products
into
diversified
compounds.
Angewandte Chemie International Edition,
Journal Year:
2019,
Volume and Issue:
58(36), P. 12486 - 12490
Published: July 11, 2019
Abstract
A
catalytic,
enantio‐,
and
diastereoselective
formation
of
sulfenyl
acetals
bearing
multiple
stereogenic
centers
is
reported.
Alkenyl
aldehydes
undergo
a
chiral
thiiranium
ion
initiated
cascade
starting
with
intramolecular
capture
by
formyl
group
termination
HFIP
solvent.
This
method
provides
one‐pot
synthesis
dihydropyran
1,3‐disubstituted
isochroman
in
good
to
excellent
yield
high
levels
diastereo‐
(up
>99:1
dr)
enantiocontrol
99:1
er).
Angewandte Chemie,
Journal Year:
2019,
Volume and Issue:
131(39), P. 13992 - 13997
Published: July 8, 2019
Abstract
Metal
hydride
catalyzed
hydrocarbonation
reactions
of
alkenes
are
an
efficient
approach
to
construct
new
carbon–carbon
bonds
from
readily
available
alkenes.
However,
the
regioselectivity
remains
challenging
be
controlled.
In
nickel
(NiH)
hydrocarbonation,
linear
selectivity
is
most
often
obtained
because
relative
stability
Ni–alkyl
intermediate
over
its
branched
counterpart.
Herein,
we
show
that
boronic
pinacol
ester
(Bpin)
group
directs
a
Ni‐catalyzed
occur
at
adjacent
carbon
center,
resulting
in
formal
branch
selectivity.
Both
alkyl
and
aryl
halides
can
used
as
electrophiles
this
providing
access
wide
range
secondary
Bpin
derivatives,
which
valuable
building
blocks
synthetic
chemistry.
The
utility
method
demonstrated
by
late‐stage
functionalization
natural
products
drug
molecules,
synthesis
anticancer
agent,
iterative
syntheses.
