The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: May 5, 2025
Enantioselective
functionalization
of
4-aminoindoles
at
the
site-specific
C7
position
via
a
chiral
phosphoric
acid-catalyzed
Friedel-Crafts
reaction
with
cyclic
thioimidates
was
developed.
This
approach
enables
formation
4,7-difunctionalized
indoles
incorporating
N,S-acetal
motif
excellent
yield
and
enantioselectivity
(up
to
99%
>99%
ee).
The
protocol
is
also
compatible
isatin-derived
ketoimines
for
highly
enantioselective
synthesis
indole
derivatives
bearing
aza-quaternary
carbon
position.
synthetic
potential
demonstrated
by
gram-scale
experiments
versatile
transformations
products,
method
characterized
low
catalyst
loading,
site
specificity,
enantioselectivity,
broad
substrate
scope.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 14, 2025
Carboranyl
amines
are
distinct
from
typical
organic
amines.
Due
to
the
electronic
influence
of
carborane
cage,
they
have
low
nucleophilicity
and
reluctant
alkylate.
Moreover,
asymmetric
synthesis
chiral
carboranes
is
still
in
its
infancy.
Herein
we
achieved
first
catalytic
N-alkylation
o-carboranyl
amine,
providing
general
access
diverse
secondary
with
high
efficiency
enantioselectivity
under
mild
conditions.
For
time,
organocatalysis
was
introduced
chemistry.
Key
success
use
situ
generated
(naphtho-)quinone
methides
as
alkylating
reagents
suitable
acid
catalysts.
This
protocol
also
applicable
S-alkylation
1-SH-o-C2B10H11.
Control
experiments
kinetic
studies
provided
important
insights
into
reaction
mechanism,
which
likely
involves
rate-determining
generation
quinone
methide
followed
by
fast
enantio-determining
nucleophilic
addition.
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.
