Alcohols as Substrates in Transition-Metal-Catalyzed Arylation, Alkylation, and Related Reactions
Chemical Reviews,
Год журнала:
2024,
Номер
124(9), С. 6078 - 6144
Опубликована: Апрель 17, 2024
Alcohols
are
abundant
and
attractive
feedstock
molecules
for
organic
synthesis.
Many
methods
their
functionalization
require
them
to
first
be
converted
into
a
more
activated
derivative,
while
recent
years
have
seen
vast
increase
in
the
number
of
complexity-building
transformations
that
directly
harness
unprotected
alcohols.
This
Review
discusses
how
transition
metal
catalysis
can
used
toward
this
goal.
These
broadly
classified
three
categories.
Deoxygenative
functionalizations,
representing
derivatization
C–O
bond,
enable
alcohol
act
as
leaving
group
formation
new
C–C
bonds.
Etherifications,
characterized
by
O–H
represent
classical
reactivity
has
been
modernized
include
mild
reaction
conditions,
diverse
partners,
high
selectivities.
Lastly,
chain
reactions
described,
wherein
acts
mediator
formal
C–H
alkyl
backbone.
Each
these
classes
transformation
will
discussed
context
intermolecular
arylation,
alkylation,
related
reactions,
illustrating
alcohols
harnessed
Язык: Английский
Copper-catalyzed regio- and stereo-selective hydrosilylation of terminal allenes to access (E)-allylsilanes
Nature Communications,
Год журнала:
2022,
Номер
13(1)
Опубликована: Июнь 27, 2022
Abstract
Regioselectivity
and
stereoselectivity
control
in
hydrosilylation
of
terminal
allenes
is
challeging.
Although
the
selective
synthesis
vinylsilanes,
branched
allylsilanes
or
linear
(
Z
)-allylsilanes
have
been
achieved,
transition-metal
catalyzed
to
access
E
)-allylsilane
difficult.
Herein,
we
report
a
copper-catalyzed
reaction
under
mild
conditions.
The
shows
broad
substrate
scope,
representing
an
efficient
method
prepare
trisubstituted
through
can
also
be
applied
disubstituted
)-allylsilanes.
mechanism
study
reveals
that
-selectivity
kinetically
controlled
by
catalyst
but
not
thermodynamically
isomerization
)-isomer.
Язык: Английский
Photoredox/Nickel-Catalyzed Diastereoselective Allylation of Aldehydes with Morita–Baylis–Hillman Adducts
ACS Catalysis,
Год журнала:
2025,
Номер
15(10), С. 8303 - 8316
Опубликована: Май 2, 2025
A
practical
diastereoselective
photoredox
nickel-mediated
allylation
of
aliphatic
and
aromatic
aldehydes
with
Morita-Baylis-Hillman
(MBH)
acetates
is
reported
here.
The
reaction
proceeds
under
visible-light
irradiation
using
MBH
derivatives,
which
are
easily
prepared
from
inexpensive
available
starting
materials,
affording
functionalized
alcohols
as
a
single
diastereoisomer
(>20:1
for
the
syn
diastereoisomer).
popular
organic
dye
3DPAFIPN
used
photocatalyst
in
combination
Hantzsch
ester
presence
catalytic
amount
stable
nickel
complexes
o-phenanthroline
ligand.
shows
broad
scope,
avoiding
use
Ni(0),
well
stoichiometric
metal
reductants
such
Zn
Mn.
relevance
was
confirmed
by
products
rapid
access
to
α-methylene-β-lactones,
useful
intermediates
synthesis
natural
or
biologically
active
relevant
products.
DFT
calculations
suggest
that
allyl
acetate-coordinated
Ni(0)
species
plays
role
catalyst
cycle
operates
through
Ni(0)-Ni(II)-Ni(I)-Ni(0)
pathway.
Язык: Английский
Nickel-Catalyzed Asymmetric Allylic Alkylation of β-Dicarbonyl Compounds via C–C Bond Activation of 2-Allylated Cyclic 1,3-Diketones
ACS Catalysis,
Год журнала:
2023,
Номер
13(3), С. 2156 - 2161
Опубликована: Янв. 25, 2023
The
asymmetric
allylic
alkylation
(AAA)
reaction
using
less
reactive,
stable
sources
is
challenging.
We
achieved
a
nickel(0)-catalyzed
AAA
of
β-dicarbonyl
compounds
under
ambient
conditions
through
unstrained
C–C
bond
activation
2-allylated
2-methylcyclohexane-1,3-dione
derivatives
to
afford
the
corresponding
quaternary
chiral
in
high
yield
with
enantioselectivity.
proceeded
almost
irreversibly
due
low
solubility
side-product,
2-methylcyclohexane-1,3-dione.
Control
experiments
and
DFT
calculations
allowed
for
elucidating
mechanism
Ni(0)-(S)-tol-MeO-BIPHEP
catalyst
system;
turnover
limiting
step
formation,
reverse
requires
7.6
kcal
mol–1
higher
energy
than
forward
reaction.
Язык: Английский
New Morita-Baylis-Hillman (MBH) phosphonium salts from alcohols to the synthesis of 2-alkenyl- and 2-alkylidenecyclohexenones
Journal of Molecular Structure,
Год журнала:
2023,
Номер
1286, С. 135532 - 135532
Опубликована: Апрель 12, 2023
Язык: Английский
Asymmetric organocatalytic Morita−Baylis−Hillman reaction and asymmetric organocatalytic transformations of Morita−Baylis−Hillman adducts. An update
Tetrahedron,
Год журнала:
2024,
Номер
172, С. 134435 - 134435
Опубликована: Дек. 23, 2024
Язык: Английский
Allylic C(sp3)−C(sp3) Bond Formation Through Pd‐Catalyzed C(sp3)−H Activation of Alkenes and 1,4‐Dienes
Advanced Synthesis & Catalysis,
Год журнала:
2022,
Номер
364(14), С. 2268 - 2288
Опубликована: Май 10, 2022
Abstract
This
review
highlights
the
allylic
C−H
alkylation
of
alkenes
(AA
H
)
with
nucleophiles
under
Pd
0
or
II
catalysis
and
achiral
chiral
conditions.
The
η
3
‐allylpalladium
intermediates
these
reactions
are
formed
from
cleavage
an
hydrogen
which
becomes
a
leaving
group,
like
acetate
moiety
allyl
acetates
during
classical
Tsuji‐Trost
procedure.
Most
cross‐dehydrogenative‐couplings
require
quinones
as
key
components;
they
may
play
role
ligand,
proton
trap
oxidant.
Efficient
asymmetric
alkylations
(AAA
’s)
have
been
performed.
diversity
procedures,
their
limitation
application
in
synthesis
underlined
well
proposed
mechanisms
with,
some
cases,
personal
comments.
data
grouped
according
to
reaction
magnified
image
Язык: Английский
An efficient one-step synthesis of a new series of mutifunctional olefins and direct hydroxymethylation of α-substituted β-keto esters
Synthetic Communications,
Год журнала:
2024,
Номер
unknown, С. 1 - 12
Опубликована: Сен. 13, 2024
Язык: Английский
Metal catalyst-free N-allylation/alkylation of imidazole and benzimidazole with Morita–Baylis–Hillman (MBH) alcohols and acetates
Beilstein Journal of Organic Chemistry,
Год журнала:
2023,
Номер
19, С. 1251 - 1258
Опубликована: Сен. 1, 2023
A
highly
α-regioselective
N-nucleophilic
allylic
substitution
of
cyclic
MBH
alcohols
and
acetates
with
imidazole
or
benzimidazole,
in
toluene
at
reflux
an
azeotropic
distillation,
was
successfully
carried
out
no
catalysts
additives,
affording
the
corresponding
N-substituted
derivatives
good
yields.
On
other
hand,
refluxing
methanol,
aza-Michael
addition
onto
acyclic
performed
using
DABCO
as
additive,
leading
to
1,4-adducts
70–84%
Язык: Английский
Metal catalyst-free N-Allylation/alkylation of Imidazole and Benzimidazole with Morita-Baylis-Hillman (MBH) alcohols and acetates
Опубликована: Май 23, 2023
A
highly
a-regioselective
N
-nucleophilic
allylic
substitutions
of
cyclic
MBH
alcohols
and
acetates
with
imidazole
or
benzimidazole,
in
toluene
at
reflux
an
azeotropic
distillation,
was
successfully
carried
out
no
catalysts
additives,
affording
the
corresponding
-substituted
derivatives
good
yields.
On
other
hand,
refluxing
methanol,
aza-Michael
additions
onto
acyclic
performed
using
DABCO
as
additive,
leading
to
1,4-adducts
70-84%
Язык: Английский