Organic Process Research & Development,
Journal Year:
2021,
Volume and Issue:
25(8), P. 1719 - 1787
Published: July 26, 2021
The
growth
and
development
of
an
extensive
range
metals
complexed
with
chiral
ligands
for
the
purpose
catalyzing
a
variety
reactions
in
enantioselective
manner
has
been
impressive
its
scope,
chemical
yields
high
ee
values.
Chief
among
classes
synthetic
transformations
that
asymmetric
reduction
prochiral
substrates.
These
include
ketones,
imines,
unsaturated
aldehydes,
esters,
nitriles
olefins,
as
well
number
coupling
reactions.
In
concert
these
efficient
catalyst
systems,
organosilanes
have
ability
to
carry
out
any
organic
reductions
under
conditions.
reactions,
which
reality
are
hydrosilylations
(hydrosilylation
considered
interchangeable
herein)
initially
resulting
silylated
product
is
hydrolyzed
ultimate
desired
functionality,
sterically
electronically
alter
organosilane
reductant
can
contribute
overall
success
transformation.
this
review,
we
present
thorough
compilation
literature
covering
use
metal-catalyzed
(hydrosilylations)
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.
Green Chemistry,
Journal Year:
2022,
Volume and Issue:
24(16), P. 6100 - 6107
Published: Jan. 1, 2022
An
unprecedented
visible-light-driven
regioselective
carbocarboxylation
of
1,3-dienes
with
CO
2
using
aryl
and
alkyl
halides
under
mild
conditions
is
reported
herein.
Organic Letters,
Journal Year:
2020,
Volume and Issue:
22(5), P. 2032 - 2037
Published: Feb. 13, 2020
We
report
the
enantioselective
formation
of
quaternary
stereogenic
centers
by
intermolecular
addition
malononitrile,
an
acyl
anion
equivalent,
and
related
pronucleophiles
to
several
1,3-disubstituted
acyclic
1,3-dienes
in
presence
a
Pd–PHOX
catalyst.
Products
are
obtained
up
88%
yield
99:1
er
most
cases
formed
as
single
regioisomer.
The
products'
malononitrile
unit
undergoes
oxidative
functionalization
afford
β,γ-unsaturated
carbonyls
bearing
internal
olefins
α-quaternary
centers.
Organic Process Research & Development,
Journal Year:
2021,
Volume and Issue:
25(8), P. 1719 - 1787
Published: July 26, 2021
The
growth
and
development
of
an
extensive
range
metals
complexed
with
chiral
ligands
for
the
purpose
catalyzing
a
variety
reactions
in
enantioselective
manner
has
been
impressive
its
scope,
chemical
yields
high
ee
values.
Chief
among
classes
synthetic
transformations
that
asymmetric
reduction
prochiral
substrates.
These
include
ketones,
imines,
unsaturated
aldehydes,
esters,
nitriles
olefins,
as
well
number
coupling
reactions.
In
concert
these
efficient
catalyst
systems,
organosilanes
have
ability
to
carry
out
any
organic
reductions
under
conditions.
reactions,
which
reality
are
hydrosilylations
(hydrosilylation
considered
interchangeable
herein)
initially
resulting
silylated
product
is
hydrolyzed
ultimate
desired
functionality,
sterically
electronically
alter
organosilane
reductant
can
contribute
overall
success
transformation.
this
review,
we
present
thorough
compilation
literature
covering
use
metal-catalyzed
(hydrosilylations)
