Although
alkyl
alcohols
and
aryl
chlorides
are
the
two
most
abundant
substrate
pools
for
cross-electrophile
coupling,
methods
to
couple
them
remain
limited.
Herein
we
demonstrate
a
simple
procedure
in
situ
deoxychlorination
of
followed
by
XEC
with
chlorides.
A
broad
scope
can
be
achieved
tuning
rate
reaction
via
halide
exchange.
Key
success
is
identification
1-chloro-N,N,2-trimethyl-1-propenylamine
as
mild,
noninterfering
halogenation
reagent.
Journal of the American Chemical Society,
Год журнала:
2021,
Номер
143(9), С. 3536 - 3543
Опубликована: Фев. 23, 2021
As
alcohols
are
ubiquitous
throughout
chemical
science,
this
functional
group
represents
a
highly
attractive
starting
material
for
forging
new
C–C
bonds.
Here,
we
demonstrate
that
the
combination
of
anodic
preparation
alkoxy
triphenylphosphonium
ion
and
nickel-catalyzed
cathodic
reductive
cross-coupling
provides
an
efficient
method
to
construct
C(sp2)–C(sp3)
bonds,
in
which
free
aryl
bromides—both
readily
available
chemicals—can
be
directly
used
as
coupling
partners.
This
paired
electrolysis
reaction
features
broad
substrate
scope
bearing
wide
gamut
functionalities,
was
illustrated
by
late-stage
arylation
several
structurally
complex
natural
products
pharmaceuticals.
Accounts of Chemical Research,
Год журнала:
2022,
Номер
55(17), С. 2491 - 2509
Опубликована: Авг. 11, 2022
ConspectusTransition-metal-catalyzed
reductive
coupling
of
electrophiles
has
emerged
as
a
powerful
tool
for
the
construction
molecules.
While
major
achievements
have
been
made
in
field
cross-couplings
between
organic
halides
and
pseudohalides,
an
increasing
number
reports
demonstrates
reactions
involving
more
readily
available,
low-cost,
stable,
but
unreactive
electrophiles.
This
account
summarizes
recent
results
our
laboratory
focusing
on
this
topic.
These
findings
typically
include
deoxygenative
C–C
alcohols,
alkylation
alkenyl
acetates,
C–Si
chlorosilanes,
C–Ge
chlorogermanes.The
alcohols
with
is
synthetically
appealing,
potential
chemistry
remains
to
be
disclosed.
Our
initial
study
focused
reaction
allylic
aryl
bromides
by
combination
nickel
Lewis
acid
catalysis.
method
offers
selectivity
that
opposite
classic
Tsuji–Trost
reactions.
Further
investigation
benzylic
led
foundation
dynamic
kinetic
cross-coupling
strategy
applications
nickel-catalyzed
arylation
cobalt-catalyzed
enantiospecific
alkenylation
alcohols.
The
titanium
catalysis
was
later
established
produce
carbon
radicals
directly
from
unactivated
tertiary
via
C–OH
cleavage.
development
their
fragments
delivers
new
methods
all-carbon
quaternary
centers.
shown
high
functionalization
leaving
primary
secondary
intact.
Alkenyl
acetates
are
inexpensive,
environmentally
friendly
considered
most
attractive
reagents.
benzyl
ammoniums
alkyl
mild
approaches
conversion
ketones
into
aliphatic
alkenes.Extensive
studies
enabled
us
extend
cross-electrophile
silicon
germanium
chemistry.
harness
ready
availability
chlorosilanes
chlorogermanes
suffer
challenge
low
reactivity
toward
transition
metals.
Under
catalysis,
broad
range
couple
well
vinyl-
hydrochlorosilanes.
use
partners
formation
functionalized
alkylsilanes.
seems
less
substrate-dependent,
various
common
aryl,
alkenyl,
In
general,
functionalities
such
Grignard-sensitive
groups
(e.g.,
acid,
amide,
alcohol,
ketone,
ester),
acid-sensitive
ketal
THP
protection),
fluoride
chloride,
bromide,
tosylate
mesylate,
silyl
ether,
amine
tolerated.
provide
access
organosilicon
organogermanium
compounds,
some
which
challenging
obtain
otherwise.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(14), С. 6185 - 6192
Опубликована: Март 30, 2022
Alcohols
and
carboxylic
acids
are
among
the
most
commercially
abundant,
synthetically
versatile,
operationally
convenient
functional
groups
in
organic
chemistry.
Under
visible
light
photoredox
catalysis,
these
native
synthetic
handles
readily
undergo
radical
activation,
resulting
open-shell
intermediates
can
subsequently
participate
transition
metal
catalysis.
In
this
report,
we
describe
C(sp3)–C(sp3)
cross-coupling
of
alcohols
through
dual
combination
N-heterocyclic
carbene
(NHC)-mediated
deoxygenation
hypervalent
iodine-mediated
decarboxylation.
This
mild
practical
Ni-catalyzed
radical-coupling
protocol
was
employed
to
prepare
a
wide
array
alkyl–alkyl
cross-coupled
products,
including
highly
congested
quaternary
carbon
centers
from
corresponding
tertiary
or
acids.
We
demonstrate
applications
methodology
alcohol
C1-alkylation
formal
homologation,
as
well
late-stage
functionalization
drugs,
natural
biomolecules.
Chemical Society Reviews,
Год журнала:
2021,
Номер
50(16), С. 8903 - 8953
Опубликована: Янв. 1, 2021
The
formation
of
C–aryl
bonds
has
been
the
focus
intensive
research
over
last
decades
for
construction
complex
molecules
from
simple,
readily
available
feedstocks.
Journal of the American Chemical Society,
Год журнала:
2021,
Номер
143(13), С. 4896 - 4902
Опубликована: Март 23, 2021
Under
mild
reaction
conditions
with
inexpensive
cerium
and
nickel
catalysts,
easily
accessible
free
alcohols
can
now
be
utilized
as
operationally
simple
robust
carbon
pronucleophiles
in
selective
C(sp3)–C(sp2)
cross-couplings.
Facilitated
by
automated
high-throughput
experimentation,
sterically
encumbered
benzoate
ligands
have
been
identified
for
complexes,
enabling
the
synergistic
cooperation
of
catalysis
emerging
metallaphotoredox
catalysis.
A
broad
range
aromatic
halides
facilely
employed
this
transformation,
representing
a
new
paradigm
bond
construction
between
aryl
extrusion
formaldehyde.
Moreover,
mechanistic
investigations
conducted,
leading
to
identification
tribenzoate
cerium(III)
complex
viable
intermediate.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(19), С. 8551 - 8559
Опубликована: Апрель 4, 2022
A
new
strategy
for
the
direct
cleavage
of
C(sp3)-OH
bond
has
been
developed
via
activation
free
alcohols
with
neutral
diphenyl
boryl
radical
generated
from
sodium
tetraphenylborate
under
mild
visible
light
photoredox
conditions.
This
verified
by
cross-electrophile
coupling
and
carbon
dioxide
synthesis
carboxylic
acids.
Direct
transformation
a
range
primary,
secondary,
tertiary
benzyl
to
acids
achieved.
Control
experiments
computational
studies
indicate
that
undergoes
homolysis
bond,
generating
alkyl
radicals.
After
reducing
into
anion
conditions,
following
carboxylation
CO2
affords
product.
Chinese Journal of Chemistry,
Год журнала:
2023,
Номер
41(13), С. 1637 - 1652
Опубликована: Янв. 23, 2023
Comprehensive
Summary
Alcohols
are
among
the
most
accessible
functionalities.
Catalytic
deoxygenative
functionalization
of
alcohols
is
highly
synthetically
appealing.
While
significant
progress
has
been
made
on
reactions
with
nucleophiles,
electrophilic
coupling
partners
remain
a
real
challenge.
This
manuscript
highlights
advance
in
this
direction,
which
mainly
achieved
by
first‐row
transition
metals.
The
low‐valent
titanium
catalyst
shown
unique
reactivity
to
homolytically
cleave
C—OH
bonds.
formed
carbon
radicals
could
either
undergo
reduction
give
protonation
products
or
couple
fragments
form
C—C
chemistry
initially
realized
using
stoichiometric
amount
reagents
and
later
extended
catalytic
variants.
Nickel
features
variety
oxidation
states
ranging
from
Ni
0
IV
,
both
two‐electron
oxidative
addition
single‐electron
process
involved
their
activation
an
electrophile.
These
properties
enable
nickel
catalyze
reductive
R–X
electrophiles.
reaction
first
reported
allylic
alcohols,
then
benzylic
and,
very
recently
non‐activated
alcohols.
Recent
effort
resulted
many
invaluable
methodologies
that
improve
efficiency
for
construction
aliphatic
use
cobalt
copper
catalysts
not
only
expands
substrate
scope
these
but
also
shows
new
selectivity
issues.
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
Chemical Reviews,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 26, 2024
Cross-electrophile
coupling
(XEC),
defined
by
us
as
the
cross-coupling
of
two
different
σ-electrophiles
that
is
driven
catalyst
reduction,
has
seen
rapid
progression
in
recent
years.
As
such,
this
review
aims
to
summarize
field
from
its
beginnings
up
until
mid-2023
and
provide
comprehensive
coverage
on
synthetic
methods
current
state
mechanistic
understanding.
Chapters
are
split
type
bond
formed,
which
include
C(sp