ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(3), P. 2135 - 2141
Published: Jan. 24, 2023
The
activation
and
functionalization
of
C–F
bonds
for
the
construction
C–C
C–X
have
drawn
significant
research
attention
in
recent
years.
However,
chemo-
stereoselective
control
dual
bond
gem-difluoroalkenes
remains
a
formidable
challenge.
Herein,
Ni-catalyzed
reductive
cross-coupling
with
alkenyl-electrophiles
D2O
that
allowed
generation
C(sp2)–C(sp2)
C(sp2)–D
one
pot
by
successive
defluorination
is
described.
This
methodology
offers
facile
access
to
various
deuterated
1,3-dienes
broad
functional
group
compatibility
(E)-selectivity
under
mild
conditions.
Preliminary
mechanistic
studies
indicate
α-alkenyl-substituted
monofluoroalkenes
might
be
intermediates
this
protocol.
Journal of the American Chemical Society,
Journal Year:
2021,
Volume and Issue:
143(32), P. 12825 - 12835
Published: Aug. 5, 2021
Ketones
are
among
the
most
widely
used
intermediates
in
organic
synthesis,
and
their
synthesis
from
inexpensive
feedstocks
could
be
quite
impactful.
Regio-
enantioselective
hydroacylation
reactions
of
dienes
provide
facile
entry
into
useful
ketone-bearing
chiral
motifs
with
an
additional
latent
functionality
(alkene)
suitable
for
further
elaboration.
Three
classes
dienes,
2-
or
4-monosubstituted
2,4-disubstituted
1,3-dienes,
undergo
cobalt(I)-catalyzed
regio-
hydroacylation,
giving
products
high
enantiomeric
ratios
(er).
These
highly
dependent
on
ligands,
we
have
identified
ligands
reaction
conditions
each
class
dienes.
2-Substituted
predominantly
1,2-addition,
whereas
4-substituted
terminal
give
4,1-
4,3-hydroacylation
depending
aldehyde,
aliphatic
aldehydes
4,1-addition
aromatic
4,3-addition.
Included
substrates
feedstock
isoprene
(US$1.4/kg)
myrcene
(US$129/kg),
several
common
aldehydes.
We
propose
oxidative
dimerization
mechanism
that
involves
a
Co(I)/Co(III)
redox
cycle
appears
to
initiated
by
cationic
Co(I)
intermediate.
Studies
using
isolated
neutral
complexes
confirm
critical
role
these
reactions.
Enantioselective
1,2-hydroacylation
2-trimethylsiloxy-1,3-diene
reveals
hitherto
undisclosed
route
siloxy-protected
aldols.
Finally,
syntheses
anti-inflammatory
drug
(S)-Flobufen
(2
steps,
92%
yield,
>99:1
er)
food
additive
(S)-Dihydrotagetone
(1
step,
83%
yield;
96:4
illustrate
power
this
method
preparation
commercially
relevant
compounds.
Organic Chemistry Frontiers,
Journal Year:
2021,
Volume and Issue:
8(24), P. 7037 - 7049
Published: Jan. 1, 2021
This
review
summarizes
the
advances
in
1,3-difunctionalization
of
alkenes
mediated
by
Pd-,
Ni-,
Fe-,
and
Cu-based
catalysts,
as
well
under
metal-free
conditions,
with
an
emphasis
on
reaction
mechanisms
factors
governing
regioselectivity.
ACS Catalysis,
Journal Year:
2022,
Volume and Issue:
12(6), P. 3651 - 3659
Published: March 7, 2022
The
synthesis
of
compounds
having
quaternary
carbon
centers
through
a
catalytic
stereo-
and
regioselective
difunctionalization
2-substituted
1,3-dienes
remains
elusive.
Here,
we
present
dual
Co/photoredox-catalyzed
cascade
approach
that
addresses
this
challenge
using
modular
vinyl
cyclic
carbonates
functioning
as
masked
2-aryl-1,3-diene
surrogates.
latter
species
are
conveniently
prepared
in
situ
converted
into
nucleophilic
Co(allyl)
intermediates
intercepted
by
aldehydes
to
afford
homoallylic
alcohols
with
ample
scope
reaction
partners.
developed
protocol
marks
significant
step
forward
the
use
structurally
versatile
their
1,2-hydroalkylation
1,2-dicarbofunctionalization.
Chemical Communications,
Journal Year:
2022,
Volume and Issue:
58(37), P. 5614 - 5617
Published: Jan. 1, 2022
Herein,
we
reported
the
first
versatile
and
expeditious
protocol
for
diversity-oriented
synthesis
(DOS)
of
fluoroalkylated
amines
via
photoinduced
palladium-catalyzed
cross
coupling
1,3-dienes,
fluoroalkyl
iodides,
which
features
excellent
3,4-
1,4-selectivity
controlled
by
a
broad
substrate
scope
as
well
good
function
group
tolerance,
could
be
extended
to
late-stage
modification
bioactive
molecules.
ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(3), P. 2135 - 2141
Published: Jan. 24, 2023
The
activation
and
functionalization
of
C–F
bonds
for
the
construction
C–C
C–X
have
drawn
significant
research
attention
in
recent
years.
However,
chemo-
stereoselective
control
dual
bond
gem-difluoroalkenes
remains
a
formidable
challenge.
Herein,
Ni-catalyzed
reductive
cross-coupling
with
alkenyl-electrophiles
D2O
that
allowed
generation
C(sp2)–C(sp2)
C(sp2)–D
one
pot
by
successive
defluorination
is
described.
This
methodology
offers
facile
access
to
various
deuterated
1,3-dienes
broad
functional
group
compatibility
(E)-selectivity
under
mild
conditions.
Preliminary
mechanistic
studies
indicate
α-alkenyl-substituted
monofluoroalkenes
might
be
intermediates
this
protocol.
