Advanced Science,
Journal Year:
2024,
Volume and Issue:
11(24)
Published: April 22, 2024
Abstract
Chiral
aldehydes
containing
a
tertiary
stereogenic
center
are
versatile
building
blocks
in
organic
chemistry.
In
particular,
such
structural
motifs
bearing
an
α,α‐diaryl
moiety
very
challenging
scaffolds
and
their
efficient
asymmetric
synthesis
is
not
reported.
this
work,
phosphoric
acid‐catalyzed
enantioselective
of
from
simple
terminal
alkynes
presented.
This
approach
yields
wide
range
highly
enolizable
good
with
excellent
enantioselectivities.
Facile
transformations
the
products,
as
well
bioactive
molecules,
including
effective
anti‐smallpox
agent
FDA‐approved
antidepressant
drug
(+)‐sertraline,
demonstrated.
Chinese Journal of Chemistry,
Journal Year:
2022,
Volume and Issue:
41(1), P. 27 - 36
Published: Sept. 16, 2022
Comprehensive
Summary
A
new
class
of
m
‐hydroxybenzyl
alcohols
has
been
designed
as
competent
three‐carbon
building
blocks
and
achieved
their
application
in
2‐indolylmethanol‐involved
regioselective
(3
+
3)
cycloadditions
under
the
catalysis
Brønsted
acids.
By
this
appoach,
a
series
indole‐fused
six‐membered
cycloadducts
have
synthesized
overall
good
yields
(up
to
98%)
with
excellent
regioselectivity
(all
>95:
5
rr),
thus
affording
powerful
method
for
construction
rings.
Moreover,
catalytic
asymmetric
version
cycloaddition
preliminarily
investigated,
which
revealed
potential
reaction
constructing
chiral
rings
an
enantioselective
manner.
This
work
not
only
accomplished
first
design
reactants,
but
also
represents
cycloadditions.
In
addition,
provides
example
C3‐nucleophilic
2‐indolylmethanols,
will
substantially
enrich
chemistry
2‐indolylmethanols.
Organic & Biomolecular Chemistry,
Journal Year:
2023,
Volume and Issue:
21(17), P. 3477 - 3502
Published: Jan. 1, 2023
This
review
article
presents
an
in-depth
analysis
of
the
strategies
and
methodologies
for
using
chiral
phosphoric
acids
as
organocatalysts
in
asymmetric
syntheses
from
recent
literature.
Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: Aug. 9, 2023
The
C-N
axially
chiral
N-arylpyrrole
motifs
are
privileged
scaffolds
in
numerous
biologically
active
molecules
and
natural
products,
as
well
ligands/catalysts.
Asymmetric
synthesis
of
N-arylpyrroles,
however,
is
still
challenging,
the
simultaneous
creation
contiguous
axial
central
chirality
remains
unknown.
Herein,
a
diastereo-
atroposelective
N-arylpyrroles
enabled
by
light-induced
phosphoric
acid
catalysis
has
been
developed.
key
transformation
one-pot,
three-component
oxo-diarylation
reaction,
which
simultaneously
creates
quaternary
stereogenic
center.
A
broad
range
unactivated
alkynes
were
readily
employed
reaction
partner
this
transformation,
products
obtained
good
yields,
with
excellent
enantioselectivities
very
diastereoselectivities.
Notably,
skeletons
represent
interesting
structural
that
could
be
used
ligands
catalysts
asymmetric
catalysis.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(23), P. 12802 - 12811
Published: June 5, 2023
Quinone
methides
are
well-established
intermediates
in
asymmetric
synthesis.
In
contrast,
their
extended
analogues
with
the
carbonyl
and
methide
units
distributed
across
two
different
rings
have
not
been
exploited
Herein,
we
achieved
first
process
involving
such
intermediates.
Specifically,
use
of
suitable
chiral
phosphoric
acids
enabled
situ
generation
2-naphthoquinone
8-methides
corresponding
aza
counterparts
for
mild
one-pot
nucleophilic
addition.
These
processes
provided
rapid
access
to
a
wide
range
previously
less
accessible
remotely
naphthols
naphthylamines
both
high
efficiency
excellent
enantioselectivity.
Control
experiment
DFT
calculations
important
insights
into
reaction
mechanism,
which
likely
involves
acid
molecules
enantiodetermining
transition
states.
This
work
serves
as
proof
concept
exploitation
new
types
quinone
versatile
synthesis,
thus
providing
platform
efficient
construction
remote
benzylic
stereogenic
centers
aromatic
compounds.
Science,
Journal Year:
2023,
Volume and Issue:
382(6668), P. 325 - 329
Published: Oct. 19, 2023
Benzylic
stereogenic
centers
are
ubiquitous
in
natural
products
and
pharmaceuticals.
A
potentially
general,
though
challenging,
approach
toward
their
selective
creation
would
be
asymmetric
unimolecular
nucleophilic
substitution
(SN1)
reactions
that
proceed
through
highly
reactive
benzylic
cations.
We
now
report
a
broadly
applicable
solution
to
this
problem
by
identifying
chiral
counteranions
pair
with
secondary
cations
engage
catalytic
C-C,
C-O,
C-N
bond-forming
excellent
enantioselectivity.
The
critical
cationic
intermediate
can
accessed
from
different
precursors
via
Lewis-
or
Brønsted
acid
catalysis.
Key
our
strategy
is
the
use
of
only
weakly
basic,
confined
posited
prolong
lifetime
carbocation,
thereby
avoiding
nonproductive
deprotonation
pathways
corresponding
styrene.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
unknown
Published: July 23, 2024
Abstract
Catalytic
enantioselective
preparation
of
alkene
atropisomers
with
multiple
stereogenic
elements
and
discovery
their
applications
have
become
significant
but
challenging
issues
in
the
scientific
community
due
to
unique
structures
this
class
atropisomers.
We
herein
report
first
catalytic
atroposelective
cyclopentenyl[
b
]indoles,
a
new
kind
atropisomers,
point
axial
chirality
via
an
unusual
rearrangement
reaction
3‐indolylmethanols
under
asymmetric
organocatalysis.
Notably,
novel
type
promising
developing
chiral
ligands
or
organocatalysts,
discovering
antitumor
drug
candidates
fluorescence
imaging
materials.
Moreover,
theoretical
calculations
elucidated
possible
mechanism
non‐covalent
interactions
control
enantioselectivity.
This
approach
offers
synthetic
strategy
for
elements,
represents
3‐indolylmethanols,
which
will
advance
chemistry
indole
chemistry.
