Enantioselective Hydroxylation of Dihydrosilanes to Si‐Chiral Silanols Catalyzed by In Situ Generated Copper(II) Species
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(32)
Опубликована: Июнь 2, 2022
Catalytic
enantioselective
hydroxylation
of
prochiral
dihydrosilanes
with
water
is
expected
to
be
a
highly
efficient
way
access
Si-chiral
silanols,
yet
has
remained
unknown
up
date.
Herein,
we
describe
strategy
for
realizing
this
reaction:
using
an
alkyl
bromide
as
single-electron
transfer
(SET)
oxidant
invoking
CuII
species
and
chiral
multidentate
anionic
N,N,P-ligands
effective
enantiocontrol.
The
reaction
readily
provides
broad
range
silanols
high
enantioselectivity
excellent
functional
group
compatibility.
In
addition,
manifest
the
synthetic
potential
by
establishing
two
schemes
transforming
obtained
products
into
compounds
structural
diversity.
Our
preliminary
mechanistic
studies
support
mechanism
involving
SET
recruiting
active
catalyst
its
subsequent
σ-metathesis
dihydrosilanes.
Язык: Английский
Rhodium‐Catalyzed Chemo‐, Regio‐ and Enantioselective Hydroformylation of Cyclopropyl‐Functionalized Trisubstituted Alkenes
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(33)
Опубликована: Июнь 18, 2022
The
first
rhodium-catalyzed
highly
chemo-,
regio-
and
enantioselective
hydroformylation
of
cyclopropyl-functionalized
trisubstituted
alkenes
affording
useful
chiral
cyclopropyl
entities
is
reported.
Compared
to
generally
used
diphosphine
ligands
for
asymmetric
catalysis,
the
modified
hybrid
phosphorus
ligand,
named
(R,S)-DTBM-Yanphos,
can
convert
a
series
readily
available
into
high-value
aldehydes
with
high
selectivities
(81-98
%
ee).
Gram-scale
reactions
(TON
up
1500)
follow-up
transformations
corresponding
alcohol,
acid,
esters
nitrile
are
also
presented.
Finally,
possible
mechanism
involving
ring-open-hydroformylation
pathways
proposed
based
on
control
deuteroformylation
reactions.
Язык: Английский
Chiral phosphoric acid-catalyzed enantioselective phosphinylation of 3,4-dihydroisoquinolines with diarylphosphine oxides
Communications Chemistry,
Год журнала:
2023,
Номер
6(1)
Опубликована: Фев. 9, 2023
Chiral
phosphorous-containing
compounds
are
playing
a
more
and
significant
role
in
several
different
research
fields.
Here,
we
show
chiral
phosphoric
acid-catalyzed
enantioselective
phosphinylation
of
3,4-dihydroisoquinolines
with
diarylphosphine
oxides
for
the
efficient
practical
construction
family
α-amino
diverse
range
functional
groups.
The
phosphine
products
suitable
transforming
to
kinds
(thio)ureas,
which
might
be
employed
as
ligands
or
catalysts
potential
applications
asymmetric
catalysis.
Control
NMR
tracking
experiments
that
reaction
proceeds
via
tert-butyl
1-(tert-butoxy)-3,4-dihydroiso-quinoline-2(1H)-carboxylate
intermediate,
followed
by
C-P
bond
formation.
Furthermore,
computational
studies
elucidated
hydrogen
bonding
strength
between
phosphonate
isoquinolinium
determines
stereoselectivity
reaction.
Язык: Английский
Expanding the Promiscuity of a Copper‐Dependent Oxidase for Enantioselective Cross‐Coupling of Indoles
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(16)
Опубликована: Фев. 15, 2023
Herein,
we
disclose
the
highly
enantioselective
oxidative
cross-coupling
of
3-hydroxyindole
esters
with
various
nucleophilic
partners
as
catalyzed
by
copper
efflux
oxidase.
The
biocatalytic
transformation
delivers
functionalized
2,2-disubstituted
indolin-3-ones
excellent
optical
purity
(90-99
%
ee),
which
exhibited
anticancer
activity
against
MCF-7
cell
lines,
shown
preliminary
biological
evaluation.
Mechanistic
studies
and
molecular
docking
results
suggest
formation
a
phenoxyl
radical
enantiocontrol
facilitated
suited
enzyme
chiral
pocket.
This
study
is
significant
regard
to
expanding
catalytic
repertoire
natural
multicopper
oxidases
well
enlarging
synthetic
toolbox
for
sustainable
asymmetric
coupling.
Язык: Английский
Enantioselective Hydroxylation of Dihydrosilanes to Si‐Chiral Silanols Catalyzed by In Situ Generated Copper(II) Species
Angewandte Chemie,
Год журнала:
2022,
Номер
134(32)
Опубликована: Июнь 2, 2022
Abstract
Catalytic
enantioselective
hydroxylation
of
prochiral
dihydrosilanes
with
water
is
expected
to
be
a
highly
efficient
way
access
Si‐chiral
silanols,
yet
has
remained
unknown
up
date.
Herein,
we
describe
strategy
for
realizing
this
reaction:
using
an
alkyl
bromide
as
single‐electron
transfer
(SET)
oxidant
invoking
Cu
II
species
and
chiral
multidentate
anionic
N,N,P‐ligands
effective
enantiocontrol.
The
reaction
readily
provides
broad
range
silanols
high
enantioselectivity
excellent
functional
group
compatibility.
In
addition,
manifest
the
synthetic
potential
by
establishing
two
schemes
transforming
obtained
products
into
compounds
structural
diversity.
Our
preliminary
mechanistic
studies
support
mechanism
involving
SET
recruiting
active
catalyst
its
subsequent
σ
‐metathesis
dihydrosilanes.
Язык: Английский
Enantio‐ and Regioselective Copper‐Catalyzed 1,2‐Dearomatization of Pyridines
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(48)
Опубликована: Окт. 11, 2023
A
copper-catalyzed
dearomative
alkynylation
of
pyridines
is
reported
with
excellent
regio-
and
enantioselectivities.
The
synthetically
valuable
enantioenriched
2-alkynyl-1,2-dihydropyridine
products
afforded
are
generated
from
the
readily
available
feedstock,
pyridine,
commercially
terminal
alkynes.
three-component
reaction
between
a
alkyne,
methyl
chloroformate
employs
copper
chloride
StackPhos,
chiral
biaryl
P,N-
ligand,
as
catalytic
system.
Under
mild
conditions,
desired
1,2-addition
delivered
in
up
to
99
%
yield
regioselectivity
ratios
25
:
1
enantioselectivities
values
ee.
Activated
non-activated
alkynes
containing
wide
range
functional
groups
well
tolerated.
Even
acetylene
gas
mono-alkynylated
high
Application
methodology
an
efficient
enantioselective
synthesis
piperidine
indolizidine,
coniceine,
reported.
Язык: Английский
Enantioselective phosphonation of isoquinolines via chiral phosphoric acid-catalyzed dearomatization
Chemical Communications,
Год журнала:
2022,
Номер
58(67), С. 9393 - 9396
Опубликована: Янв. 1, 2022
An
efficient
and
enantioselective
phosphonation
of
isoquinolines
via
chiral
phosphoric
acid-catalyzed
dearomatization
has
been
developed.
Язык: Английский
Expanding the Promiscuity of a Copper‐Dependent Oxidase for Enantioselective Cross‐Coupling of Indoles
Angewandte Chemie,
Год журнала:
2023,
Номер
135(16)
Опубликована: Фев. 15, 2023
Abstract
Herein,
we
disclose
the
highly
enantioselective
oxidative
cross‐coupling
of
3‐hydroxyindole
esters
with
various
nucleophilic
partners
as
catalyzed
by
copper
efflux
oxidase.
The
biocatalytic
transformation
delivers
functionalized
2,2‐disubstituted
indolin‐3‐ones
excellent
optical
purity
(90–99
%
ee
),
which
exhibited
anticancer
activity
against
MCF‐7
cell
lines,
shown
preliminary
biological
evaluation.
Mechanistic
studies
and
molecular
docking
results
suggest
formation
a
phenoxyl
radical
enantiocontrol
facilitated
suited
enzyme
chiral
pocket.
This
study
is
significant
regard
to
expanding
catalytic
repertoire
natural
multicopper
oxidases
well
enlarging
synthetic
toolbox
for
sustainable
asymmetric
coupling.
Язык: Английский
Enantio‐ and Regioselective Copper‐Catalyzed 1,2‐Dearomatization of Pyridines
Angewandte Chemie,
Год журнала:
2023,
Номер
135(48)
Опубликована: Окт. 11, 2023
Abstract
A
copper‐catalyzed
dearomative
alkynylation
of
pyridines
is
reported
with
excellent
regio‐
and
enantioselectivities.
The
synthetically
valuable
enantioenriched
2‐alkynyl‐1,2‐dihydropyridine
products
afforded
are
generated
from
the
readily
available
feedstock,
pyridine,
commercially
terminal
alkynes.
three‐component
reaction
between
a
alkyne,
methyl
chloroformate
employs
copper
chloride
StackPhos,
chiral
biaryl
P
,
N‐
ligand,
as
catalytic
system.
Under
mild
conditions,
desired
1,2‐addition
delivered
in
up
to
99
%
yield
regioselectivity
ratios
25
:
1
enantioselectivities
values
ee.
Activated
non‐activated
alkynes
containing
wide
range
functional
groups
well
tolerated.
Even
acetylene
gas
mono‐alkynylated
high
Application
methodology
an
efficient
enantioselective
synthesis
piperidine
indolizidine,
coniceine,
reported.
Язык: Английский
Rhodium‐Catalyzed Chemo‐, Regio‐ and Enantioselective Hydroformylation of Cyclopropyl‐Functionalized Trisubstituted Alkenes
Angewandte Chemie,
Год журнала:
2022,
Номер
134(33)
Опубликована: Июнь 18, 2022
Abstract
The
first
rhodium‐catalyzed
highly
chemo‐,
regio‐
and
enantioselective
hydroformylation
of
cyclopropyl‐functionalized
trisubstituted
alkenes
affording
useful
chiral
cyclopropyl
entities
is
reported.
Compared
to
generally
used
diphosphine
ligands
for
asymmetric
catalysis,
the
modified
hybrid
phosphorus
ligand,
named
(
R
,
S
)‐DTBM‐Yanphos,
can
convert
a
series
readily
available
into
high‐value
aldehydes
with
high
selectivities
(81–98
%
ee
).
Gram‐scale
reactions
(TON
up
1500)
follow‐up
transformations
corresponding
alcohol,
acid,
esters
nitrile
are
also
presented.
Finally,
possible
mechanism
involving
ring‐open‐hydroformylation
pathways
proposed
based
on
control
deuteroformylation
reactions.
Язык: Английский