Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(22), P. 3955 - 3959
Published: May 27, 2022
The
highly
enantioselective
transfer
hydrogenation
of
benzoxazinones
with
chiral
phosphoric
acids
under
H2
was
successfully
achieved,
where
boranes
promoted
the
phenanthridine
for
regeneration
dihydrophenanthridine
as
hydrogen
donor.
A
variety
dihydrobenzoxazinones
were
obtained
in
high
yields
up
to
99%
ee.
current
work
provides
a
promising
solution
unreactive
substrates
frustrated
Lewis
pair-catalyzed
asymmetric
hydrogenation.
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 8, 2025
An
enantioselective
synthesis
of
2-aryl
3,3-disubstituted
3H-indoles
has
been
successfully
developed
via
a
deracemization
process
involving
borane-catalyzed
hydrogenation
and
chiral
phosphoric-acid-catalyzed
asymmetric
transfer
hydrogenation.
A
variety
were
effective
substrates
to
afford
the
desired
indolines
in
86-95%
yields
with
45-92%
ee's.
Accounts of Chemical Research,
Journal Year:
2023,
Volume and Issue:
56(15), P. 2096 - 2109
Published: July 13, 2023
ConspectusIn
nature,
the
coenzyme
NAD(P)H
is
utilized
for
transfer
of
hydrogen
and
electrons
in
biocatalytic
reduction,
which
involves
process
recycling,
usage,
reduction.
Inspired
by
biological
system,
a
series
nonregenerable
achiral
chiral
models
were
synthesized
employed.
However,
this
approach
faced
intractable
limitations,
such
as
need
an
equivalent
amount
mimics,
accompanied
production
byproducts,
resulted
poor
atom
economy
difficult
separation
products.
Therefore,
development
new
efficient
methodologies
synthesis,
regeneration,
application
organic
synthesis
greatly
desired.To
tackle
these
challenges,
regenerable
designed
based
on
principles
reduction
applied
them
biomimetic
asymmetric
(BMAR)
reactions.
This
Account
summarizes
our
endeavors
rational
design,
models.
First,
we
will
introduce
design
(dihydrophenanthridine
dihydropyrroloquinoxaline),
successfully
to
BMAR
imines
heteroaromatics
using
homogeneous
ruthenium
complex
regeneration
catalyst,
phosphoric
acid
terminal
reductant.
Regenerable
require
addition
catalysts
or
ligands
stereoselective
control
during
process.
screening
tedious.
Narrow
substrate
scope
further
limited
their
synthesis.
(CYNAM
FENAM)
with
planar
chirality,
commercially
available
Brønsted
acids,
Lewis
organocatalysts
catalyst.
Notably,
original
factor
enantioselective
from
In
addition,
strategy
could
also
realize
myriad
electron-deficient
tetrasubstituted
alkenes,
are
challenging
substrates
transition
metal
catalyzed
hydrogenation.
methodology
provides
building
blocks
bioactive
molecules.
Finally,
detailed
mechanism
BMAR,
models,
was
elaborated
through
combination
experiments
density
functional
theory
calculations.
summary,
believe
that
results
presented
hold
significant
implications
beyond
work
have
potential
applications
field
catalysis
synthetic
methodology.
Advanced Functional Materials,
Journal Year:
2024,
Volume and Issue:
34(47)
Published: April 15, 2024
Abstract
Many
of
the
functions
and
features
practically
useful
materials
are
province
molecular‐level
chemistry
their
modulation
at
different
length‐scale.
This
report
illustrates
behind
[2.2]paracyclophane‐based
with
a
particular
focus
on
most
recent
explorations
through‐space
conjugated
small‐molecule
organic
emitters,
π‐stacked
macrocyclic
molecules
polymers,
poly(p‐phenylenevinylene)s
featuring
well‐defined
donor‐acceptors
sequence
control,
surface
engineering
technologically‐relevant
parylenes
that
finds
broad
applications
across
field
chemical
science
technology.
largely
deals
potential
opportunities
associated
molecular
planar
chirality,
conformational
behaviors,
strain‐induced
non‐planarity
aromatics,
profound
impacts
conjugation
π‐electron
interactions/delocalization
optoelectronic
properties
π‐conjugated
polymers
extended
structures
consisting
cyclophanes.
A
special
is
put
concept
supramolecular
using
chemically‐programmed
chiral
cyclophanes
via
non‐covalent
stacking
controlled
arrangements.
Illustrating
cyclophane
as
precursors/monomers
fabrication
strategies
for
incorporation
in
structurally‐controlled
(poly(
p
‐xylylene)s
formed
vapor
deposition
polymerization
post‐deposition
interface
described.
Demonstrating
rather
approach
electronically‐dictated
ring‐opening
metathesis
employing
strained
cyclophane‐diene
precursors
generate
poly(
‐phenylenevinylene)s
(i.e.,
low
dispersity)
donor‐acceptor
control
also
discussed.
will
serve
an
indispensable
one‐stop
reference
organic,
polymer
chemists,
well
material
scientists
working
research
innovations.
Organic Letters,
Journal Year:
2021,
Volume and Issue:
23(23), P. 9112 - 9117
Published: Nov. 12, 2021
Biomimetic
asymmetric
reduction
of
2-functionalized
quinolines
has
been
successfully
developed
with
the
chiral
and
regenerable
NAD(P)H
model
CYNAM
in
presence
transfer
catalyst
simple
achiral
phosphoric
acids,
providing
tetrahydroquinolines
up
to
99%
ee.
Using
this
methodology
as
a
key
step,
potent
opioid
analgesic
containing
1,2,3,4-tetrahydroquinoline
motif
was
synthesized
high
overall
yield.
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(2), P. 675 - 680
Published: Jan. 10, 2022
Asymmetric
hydrogenation
of
tetrasubstituted
alkenes
remains
a
formidable
challenge
in
asymmetric
catalysis.
We
report
herein
an
unprecedented
Rh-catalyzed
enantioselective
and
diastereoselective
easily
accessed
α,β-disubstituted
unsaturated
lactams
to
afford
synthetically
valuable
chiral
with
1,2-consecutive
stereocenters.
The
reaction
could
be
performed
on
the
gram
scale,
products
concisely
transformed
enantiomerically
pure
trans-3,4-disubstituted
piperidines,
which
are
prevalent
structural
units
medicinal
agents.
Chemical Communications,
Journal Year:
2022,
Volume and Issue:
58(24), P. 3973 - 3976
Published: Jan. 1, 2022
A
novel
transfer-catalyst-free
biomimetic
reduction
of
the
tetrasubstituted
olefins
3-sulfonyl
coumarins
with
chiral
and
regenerable
[2.2]paracyclophane-based
NAD(P)H
model
CYNAM
has
been
developed,
affording
dihydrocoumarins
excellent
enantioselectivities.
