Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 11, 2024
Chiral
2-azetines
and
allenes
are
highly
valuable
structural
units
in
natural
products
useful
chemicals.
However,
enantioselective
synthesis
of
both
has
been
extremely
challenging.
Herein,
we
present
asymmetric
construction
chiral
(70-98
%
yields
up
to
96
ee)
through
phosphine-catalyzed
[2+2]
annulation
yne-enones
with
sulfamate-derived
cyclic
imines.
These
were
easily
transformed
into
upon
treatment
Et
Chemistry - A European Journal,
Год журнала:
2024,
Номер
30(39)
Опубликована: Май 7, 2024
Axially
chiral
cycloalkylidenes
are
interesting
but
less
developed
axially
molecules.
Here,
a
bispidine-based
amine
catalytic
system
was
to
promote
efficiently
the
asymmetric
Knoevenagel
condensation
of
N-protected
oxindoles
and
benzofuranones
with
4-substituted
cyclohexanones.
A
variety
alkylidenecycloalkanes
stable
axial
chirality
were
obtained
in
good
yields
fairly
er
(enantiomeric
ratio).
Based
on
absolute
configuration
determination
product
DFT
calculations,
possible
mechanism
stereoselective
induction
proposed.
Organocatalytic
enantioselective
formal
nucleophilic
substitution
reactions
of
α-(2-hydroxynaphthalen-8-yl)propargyl
alcohols
with
1-(1H-indol-3-yl)naphthalen-2-ols
have
been
established
for
the
first
time.
With
aid
a
suitable
chiral
phosphoric
acid,
alkynyl
8-methylenenaphthalen-2(8H)-one
was
formed
in
situ
from
corresponding
alcohol,
followed
by
1,6-conjugate
additions
to
afford
number
enantioenriched
(Ra,Sc)-2,3-disubstituted
indoles
50-80%
yields
81-93%
ee
and
(Sa,Sc)-2,3-disubstituted
18-40%
79-96%
ee.
Notably,
these
products
were
characterized
presence
functional
groups,
including
indole,
naphthol,
units,
while
exhibiting
both
axial
central
chirality.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
62(4)
Опубликована: Ноя. 22, 2022
A
chiral
Brønsted
acid
catalysed
phosphine-mediated
deoxygenation
protocol
is
reported.
This
metal-free
method
provides
a
precise
kinetic
resolution
platform
for
azaarylethynyl
tertiary
alcohols,
which
are
broad
category
of
biologically
and
synthetically
important
azaarene
derivatives.
In
addition
to
providing
an
efficient
the
first
asymmetric
preparation
these
strategy
facilitates
construction
azaaryl-functionalized
allenes
with
good
excellent
enantioselectivities.
The
high
selectivity
factors
(s
up
235),
substrate
scope,
ability
convert
azaaryl
compounds
into
both
alcohols
robustly
underscore
efficiency
promising
utility
this
method.
practicability
further
validated
by
successful
synthesis
deuterated
ee
values
substantial
incorporation
deuterium
using
inexpensive
D2
O
as
source.
Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
365(12), С. 1926 - 1933
Опубликована: Май 17, 2023
Abstract
Conjugate
addition
is
one
of
the
most
powerful
and
practical
methods
for
formation
carbon‐carbon
carbon‐heteroatom
bonds
in
organic
synthesis.
Owing
to
rapid
development
asymmetric
catalysis,
significant
progress
has
been
made
field
conjugate
addition,
such
as
1,4‐addition
1,6‐addition.
However,
formidable
challenge
controlling
chemo‐,
regio‐
stereoselectivity
arises
with
extended
conjugated
systems.
Recently,
aid
Brønsted
acids
functionalized
benzyl
alcohols
indolylmethanols
successfully
developed
suitable
precursors
electron‐deficient
systems
organocatalytic
remote
stereocontrolled
additions.
This
review
investigates
advances
enantioselective
1,8‐conjugate
1,10‐conjugate
situ
formed
from
alcohols,
which
organized
according
substrates.
Chemical Communications,
Год журнала:
2023,
Номер
60(7), С. 831 - 834
Опубликована: Дек. 15, 2023
We
herein
report
regio-
and
enantioselective
arylation
of
β,γ-alkynyl-α-imino
esters
with
pyrroloisoquinolines.
Using
chiral
phosphoric
acid
catalysts,
a
wide
range
novel
axially
tetrasubstituted
α-amino
allenoates
were
accessed
in
good
yields
excellent
enantioselectivities.
Notably,
this
transformation
occurred
preferentially
at
the
sterically
more
hindered
C1-position
The
potential
scalability
late-stage
functionalization
demonstrated
utility
current
protocol.
Organic Letters,
Год журнала:
2024,
Номер
26(1), С. 396 - 400
Опубликована: Янв. 2, 2024
Despite
the
enormous
developments
in
asymmetric
transformations
of
indole
imine
methides
(IIMs),
remote
induction
involving
IIMs
remains
challenging
due
to
spatial
interaction
requirement
between
substrate
and
catalyst.
Herein
we
report
first
catalytic
nucleophilic
addition
5-methide
(5-IIM),
only
topological
isomer
whose
unknown.
stereocontrol,
high
efficiency
respectable
enantioselectivity
were
achieved
provide
access
a
range
enantioenriched
indole-containing
triaryl
alkanes.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(29)
Опубликована: Май 3, 2024
Abstract
The
chemistry
of
quinone
methides
formed
in
situ
has
been
flourishing
recent
years.
In
sharp
contrast,
the
development
and
utilization
biphenyl
are
rare.
this
study,
we
achieved
a
remote
stereocontrolled
1,12‐conjugate
addition
for
first
time.
presence
suitable
chiral
phosphoric
acid,
alkynyl
were
generated
from
α‐[4‐(4‐hydroxyphenyl)phenyl]propargyl
alcohols,
followed
by
enantioselective
with
indole‐2‐carboxylates.
strategy
enabled
alcohols
to
serve
as
efficient
allenylation
reagents,
providing
practical
access
broad
range
axially
allenes
bearing
(1,1′‐biphenyl)‐4‐ol
unit,
which
previously
less
accessible.
Combined
control
experiments,
density
functional
theory
calculations
shed
light
on
reaction
mechanism,
indicating
that
enantioselectivity
originates
nucleophilic
methides.
Notably,
not
only
versatile
intermediates
was
confirmed
but
also
organocatalytic
1,12‐addition
established.
Asian Journal of Organic Chemistry,
Год журнала:
2022,
Номер
11(9)
Опубликована: Июль 26, 2022
Abstract
A
chiral
phosphoric
acids
catalyzed
regio‐
and
enantioselective
1,10‐conjugate
addition
of
2‐arylindoles
to
alkynyl
indole
imine
methides
formed
in
situ
from
α‐(6‐indolyl)propargylic
alcohols
has
been
developed.
With
the
established
system,
organocatalytic
asymmetric
3‐allenylation
indoles
was
realized,
affording
a
broad
scope
axially
tetrasubstituted
allenes
bearing
two
motifs
high
yields
with
stereoselectivities.
Importantly,
remote
stereocontrolled
strategy
disclosed
via
for
first
time.
Organic Letters,
Год журнала:
2022,
Номер
24(43), С. 7955 - 7960
Опубликована: Окт. 24, 2022
Supramolecular
asymmetric
catalysis
has
arisen
from
the
in-depth
intersection
of
supramolecular
chemistry
and
due
to
its
unique
advantages
in
building
chiral
catalyst
libraries
regulating
performance
catalysts.
Herein,
we
combine
crown
ether
based
host-guest
with
phosphoric
acid
mediated
actualize
regulation
catalytic
two-component
tandem
acetalization
reactions.
By
comparison
reaction
without
interaction,
improvement
up
72%
yield
increases
13%
enantioselectivity
were
acquired
after
addition
alkali
metal
guests,
which
demonstrated
great
this
strategy.
