Chemistry - A European Journal,
Год журнала:
2022,
Номер
28(46)
Опубликована: Июнь 2, 2022
Abstract
The
aza‐
ortho
‐quinone
methide
(aza‐
o
‐QM)
chemistry
has
overwhelmingly
progressed
in
the
past
few
decades.
This
review
aims
to
integrate
various
transition
metal‐catalyzed
and
organocatalytic
strategies
taming
aza
‐o‐
QM
intermediates,
including
‐vinylidene
quinone
‐VQM),
‐alkynyl
‐AQM),
para
p
‐QM),
indole‐based
‐QM
analog.
These
transient
species
are
often
utilized
for
direct
enantioselective
synthesis
of
complex
(hetero)polycyclic
or
fused‐ring
molecular
scaffolds
such
as
tetrahydroquinoline
indoline,
among
others,
which
abundant
many
natural
products,
bioactive
compounds,
pharmaceuticals.
Angewandte Chemie International Edition,
Год журнала:
2020,
Номер
59(45), С. 19820 - 19824
Опубликована: Авг. 21, 2020
Herein
we
describe
the
first
organocatalytic
asymmetric
C(sp2
)-H
allylation
of
racemic
trisubstituted
allenoates
with
Morita-Baylis-Hillman
(MBH)
carbonates
to
access
axially
chiral
tetrasubstituted
allenoates.
Various
and
MBH
were
well
tolerated
under
mild
reaction
conditions,
providing
novel
adjacent
axial
chirality
tertiary
carbon
stereocenters
in
high
yields
good
excellent
diastereoselectivities
enantioselectivities.
Organic Letters,
Год журнала:
2021,
Номер
23(17), С. 6606 - 6611
Опубликована: Авг. 13, 2021
The
highly
regio-,
diastereo-,
and
enantioselective
dearomatization
reaction
of
1-substituted
2-naphthols
β,γ-alkynyl-α-imino
esters
with
complete
atom
economy
is
disclosed
via
chiral
phosphoric
acid
catalysis.
This
protocol
provides
facile
efficient
access
to
asymmetric
construction
a
broad
range
axially
allene-derived
naphthalenones
bearing
quaternary
stereocenters
in
good
yields
high
diastereoselectivities
enantioselectivities.
Organic Chemistry Frontiers,
Год журнала:
2021,
Номер
8(6), С. 1243 - 1248
Опубликована: Янв. 1, 2021
The
chiral
phosphoric
acid
catalyzed
regio-,
diastereo-
and
enantioselective
reaction
of
isoxazol-5(4H)-ones
with
β,γ-alkynyl-α-imino
esters
has
been
developed.
Organic Chemistry Frontiers,
Год журнала:
2022,
Номер
9(5), С. 1234 - 1240
Опубликована: Янв. 1, 2022
Chiral
phosphoric
acid
has
been
utilized
for
covalent
activation
of
propargylic
alcohols
to
act
as
pre-catalyst.
With
this
mode,
a
range
highly
regio-
and
enantioenriched
heterocyclic
products
could
be
generated
efficiently
from
racemic
alcohols.
Organic Letters,
Год журнала:
2022,
Номер
24(27), С. 4914 - 4918
Опубликована: Июнь 30, 2022
An
asymmetric
organocatalytic
remote
1,10-addition
of
alkynyl
indole
imine
methides
generated
in
situ
from
α-(6-indolyl)
propargylic
alcohols
with
thiazolones
has
been
developed
for
the
first
time,
affording
axially
chiral
tetrasubstituted
allenes
featuring
vicinal
sulfur-containing
quaternary
carbon
stereocenters
high
yields
excellent
stereoselectivities.
The
representative
scale-up
reaction
and
transformations
1,10-adduct
were
examined.
mechanism
was
expounded
by
control
experiments
DFT
calculations.
Organic Letters,
Год журнала:
2022,
Номер
24(18), С. 3319 - 3324
Опубликована: Май 4, 2022
A
novel
organocatalytic
asymmetric
formal
[3
+
2]
cycloaddition
of
3-substituted
1H-indoles
with
in
situ
generated
3-hydroxy-isoindolinone-derived
β,γ-alkynyl-α-ketimines
has
been
developed.
variety
biologically
relevant
chiral
spiro-isoindolinone-indolines
were
achieved
excellent
yields
(up
to
99%)
and
enantioselectivity
99%
ee)
under
mild
conditions.
The
gram-scale
reaction
this
methodology
several
interesting
transformations
the
products
have
demonstrated.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(26), С. 14562 - 14569
Опубликована: Июнь 21, 2023
Catalytic
enantioselective
construction
of
optically
active
tetraarylmethanes
remains
a
challenging
issue
in
the
field
asymmetric
synthesis
because
overwhelming
steric
hindrance
and
formidable
stereocontrol
that
existed
all-aryl-substituted
quaternary
carbon
stereocenter.
Here,
we
reported
an
organocatalytic
chiral
from
racemic
tertiary
alcohols.
With
aid
phosphoric
acid
catalyst,
6-methylenenaphthalen-2(6H)-ones
were
generated
situ
6-(hydroxydiarylmethyl)naphthalen-2-ols,
followed
by
stereoselective
1,8-conjugate
addition
to
afford
corresponding
high
excellent
yields
with
enantioselectivities.
Furthermore,
scope
alcohols
has
been
successfully
enlarged
6-(hydroxydiphenylmethyl)naphthalen-2-amines.
Notably,
it
is
first
time
use
2-naphthol/naphthalen-2-amine
unit
as
auxiliary
group
generate
α,β,γ,δ,ε,ζ-conjugate
systems,
which
have
involved
remote
stereocontrolled
reactions.
Particularly,
stereoconvergent
formal
nucleophilic
substitution
reaction
triarylmethanols
achieved
for
tetraarylmethanes.
In
addition,
DFT
calculations
applied
provide
guidance
design
additional
understand
origin
stereoselectivity.
Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
365(9), С. 1332 - 1384
Опубликована: Март 14, 2023
Abstract
Conjugated
and
non‐conjugated
allenones
appear
as
recurring
motifs
in
organic
synthesis,
natural
products
mechanistic
investigations
showing
unique
properties
applications.
The
ability
of
to
build
cycles
has
provided
a
direct
access
strained
systems,
medium‐sized
rings,
arenes,
heterocycles
complex
polycycles.
In
addition,
have
served
models
catalysis.
critic
compilation
herein
presented
will
provide
an
exhaustive
overview
the
synthetic
possibilities
may
offer,
which
certainly
inspire
our
community
their
search
more
efficient
methodologies,
preparation
biological
pharmaceutical
targets,
improve
knowledge
theoretical
chemistry.
Great
part
this
review
discuss
aspects,
catalysis
innovation
insights
chemical
transformations
implying
allenone
motif.
many
examples
on
total
synthesis
pharmacologically
active
compounds
be
described.
We
hope
that
attractive
chemistry,
catalysis,
medicinal
chemistry
communities.
magnified
image
Organic Letters,
Год журнала:
2020,
Номер
22(17), С. 6873 - 6878
Опубликована: Авг. 18, 2020
Herein,
we
report
an
enantioselective
dehydrative
γ-arylation
of
α-indolyl
propargylic
alcohols
with
phenols
via
organocatalysis,
which
provides
efficient
access
to
chiral
tetrasubstituted
allenes
and
naphthopyrans
in
high
yields
excellent
regio-
enantioselectivities
under
mild
conditions.
This
method
features
the
use
cheaply
available
naphthols/phenols
as
C–H
aryl
source
liberating
water
sole
byproduct.
Control
experiments
suggest
that
enantioselectivity
remote
regioselectivity
stem
from
dual
hydrogen-bonding
interaction
phosphoric
acid
catalyst.
