Organic Letters,
Journal Year:
2018,
Volume and Issue:
21(1), P. 70 - 74
Published: Dec. 24, 2018
A
general
and
selective
metal-catalyzed
conversion
of
biomass-derived
primary
diols
amines
to
the
highly
valuable
2,5-unsubstituted
pyrroles
has
been
developed.
The
reaction
is
catalyzed
by
a
stable
nonprecious
manganese
complex
(1
mol
%)
in
absence
organic
solvents
whereby
water
molecular
hydrogen
are
only
side
products.
catalyst
shows
unprecedented
selectivity,
avoiding
formation
pyrrolidines,
cyclic
imides,
lactones.
Chemical Reviews,
Journal Year:
2022,
Volume and Issue:
122(6), P. 6634 - 6718
Published: Feb. 18, 2022
Organic
compounds
labeled
with
hydrogen
isotopes
play
a
crucial
role
in
numerous
areas,
from
materials
science
to
medicinal
chemistry.
Indeed,
while
the
replacement
of
by
deuterium
gives
rise
improved
absorption,
distribution,
metabolism,
and
excretion
(ADME)
properties
drugs
enables
preparation
internal
standards
for
analytical
mass
spectrometry,
use
tritium-labeled
is
key
technique
all
along
drug
discovery
development
pharmaceutical
industry.
For
these
reasons,
interest
new
methodologies
isotopic
enrichment
organic
molecules
extent
their
applications
are
equally
rising.
In
this
regard,
Review
intends
comprehensively
discuss
developments
area
over
last
years
(2017–2021).
Notably,
besides
fundamental
isotope
exchange
(HIE)
reactions
isotopically
analogues
common
reagents,
plethora
reductive
dehalogenative
deuteration
techniques
other
transformations
incorporation
emerging
now
part
labeling
toolkit.
ACS Central Science,
Journal Year:
2021,
Volume and Issue:
7(4), P. 570 - 585
Published: March 25, 2021
Borrowing
hydrogen
is
a
process
that
used
to
diversify
the
synthetic
utility
of
commodity
alcohols.
A
catalyst
first
oxidizes
an
alcohol
by
removing
form
reactive
carbonyl
compound.
This
intermediate
can
undergo
diverse
range
subsequent
transformations
before
returns
"borrowed"
liberate
product
and
regenerate
catalyst.
In
this
way,
alcohols
may
be
as
alkylating
agents
whereby
sole
byproduct
one-pot
reaction
water.
recent
decades,
significant
advances
have
been
made
in
area,
demonstrating
many
effective
methods
access
valuable
products.
outlook
highlights
diversity
metal
biocatalysts
are
available
for
approach,
well
various
performed,
focusing
on
selection
most
advances.
By
succinctly
describing
conveying
versatility
borrowing
chemistry,
we
anticipate
its
uptake
will
increase
across
wider
scientific
audience,
expanding
opportunities
further
development.
Chemical Society Reviews,
Journal Year:
2022,
Volume and Issue:
51(11), P. 4386 - 4464
Published: Jan. 1, 2022
The
emerging
field
of
organometallic
catalysis
has
shifted
towards
research
on
Earth-abundant
transition
metals
due
to
their
ready
availability,
economic
advantage,
and
novel
properties.
In
this
case,
manganese,
the
third
most
abundant
transition-metal
in
Earth's
crust,
emerged
as
one
leading
competitors.
Accordingly,
a
large
number
molecularly-defined
Mn-complexes
been
synthesized
employed
for
hydrogenation,
dehydrogenation,
hydroelementation
reactions.
regard,
catalyst
design
is
based
three
pillars,
namely,
metal-ligand
bifunctionality,
ligand
hemilability,
redox
activity.
Indeed,
developed
catalysts
not
only
differ
chelating
atoms
they
possess
but
also
working
principles,
thereby
different
turnover
numbers
product
molecules.
Hence,
critical
assessment
molecularly
defined
manganese
terms
atoms,
reaction
conditions,
mechanistic
pathway,
significant.
Herein,
we
analyze
complexes
catalytic
activity,
versatility
allow
multiple
transformations
routes
convert
substrates
target
This
article
will
be
helpful
get
significant
insight
into
design,
aiding
design.
Chemical Reviews,
Journal Year:
2024,
Volume and Issue:
124(9), P. 6078 - 6144
Published: April 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
Angewandte Chemie International Edition,
Journal Year:
2019,
Volume and Issue:
59(1), P. 215 - 220
Published: Oct. 25, 2019
Highly
selective
β-methylation
of
alcohols
was
achieved
using
an
earth-abundant
first
row
transition
metal
in
the
air
stable
molecular
manganese
complex
[Mn(CO)
Angewandte Chemie International Edition,
Journal Year:
2019,
Volume and Issue:
59(4), P. 1485 - 1490
Published: Nov. 19, 2019
Abstract
We
report
an
earth‐abundant‐metal‐catalyzed
double
and
single
methylation
of
alcohols.
A
manganese
catalyst,
which
operates
at
low
catalyst
loadings
short
reaction
times,
mediates
these
reactions
efficiently.
broad
scope
primary
secondary
alcohols,
including
purely
aliphatic
examples,
1,2‐aminoalcohols
can
be
methylated.
Furthermore,
alcohol
for
the
synthesis
pharmaceuticals
has
been
demonstrated.
The
system
tolerates
many
functional
groups
among
them
hydrogenation‐sensitive
examples
upscaling
is
easily
achieved.
Mechanistic
investigations
are
indicative
a
borrowing
hydrogen
or
autotransfer
mechanism
involving
bimetallic
K‐Mn
catalyst.
accepts
as
proton
hydride
from
alcohols
efficiently
reacts
with
chalcone
via
transfer.
ACS Catalysis,
Journal Year:
2019,
Volume and Issue:
9(9), P. 8575 - 8580
Published: Aug. 21, 2019
Herein
we
report
the
iron-catalyzed
β-C(sp3)-methylation
of
primary
alcohols
using
methanol
as
a
C1
building
block.
This
borrowing
hydrogen
approach
employs
well-defined
bench-stable
(cyclopentadienone)iron(0)
carbonyl
complex
precatalyst
(5
mol
%)
and
enables
diverse
selection
substituted
2-arylethanols
to
undergo
in
good
isolated
yields
(24
examples,
65%
average
yield).
Organometallics,
Journal Year:
2019,
Volume and Issue:
38(8), P. 1815 - 1825
Published: April 12, 2019
The
application
of
nontoxic,
earth-abundant
transition
metals
in
place
costly
noble
is
a
paramount
goal
catalysis
and
especially
interesting
if
the
air-
moisture-stable
ligand
scaffold
used.
Herein,
we
report
synthesis
amines/imines
directly
from
alcohol
amines
via
hydrogen
autotransfer
or
acceptorless
dehydrogenation
catalyzed
by
well-defined
phosphine-free
Mn
complexes.
Both
imines
can
be
obtained
same
set
alcohols
using
catalyst,
only
tuning
reaction
conditions.
amount
nature
base
are
found
to
highly
important
aspect
for
observed
selectivity.
primary
secondary
have
been
employed
as
substrates
N-alkylation
reaction.
As
highlight,
showed
chemoselective
resveratrol
derivatives.
Furthermore,
Mn-catalyzed
dehydrogenative
structurally
2,3-dihydro-1H-perimidines
has
also
demonstrated.
Density
functional
theory
calculations
were
carried
out
model
path
calculate
profile.
The Journal of Organic Chemistry,
Journal Year:
2019,
Volume and Issue:
84(23), P. 15389 - 15398
Published: Nov. 8, 2019
Herein,
we
report
commercially
available
carbon-supported-palladium
(Pd/C)-catalyzed
N-methylation
of
nitroarenes
and
amines
using
MeOH
as
both
a
C1
H2
source.
This
transformation
proceeds
with
high
atom-economy
in
an
environmentally
friendly
way
via
borrowing
hydrogen
mechanism.
A
total
>30
structurally
diverse
N-methylamines,
including
bioactive
compounds,
were
selectively
synthesized
isolated
yields
up
to
95%.
Furthermore,
selective
deuteration
nimesulide,
nonsteroidal
anti-inflammatory
drug,
realized
through
the
late-stage
functionalization.