Precise Control of Regioselective N1 and N2-Alkylation of Benzotriazoles with α-Diazoacetates by Metalloporphyrin
Inorganic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 2, 2025
Regioselective
Язык: Английский
Highly diastereoselective and enantioselective cyclopropanation of alkenes catalyzed by a chiral iridium(III) porphyrin complex
Chem Catalysis,
Год журнала:
2025,
Номер
unknown, С. 101262 - 101262
Опубликована: Фев. 1, 2025
Язык: Английский
Designing Ruthenium Phthalocyanine with Chiral Pockets Formed by (1R,2S,5R)-Menthoxy Groups for Enantioselective Catalysis
ACS Catalysis,
Год журнала:
2025,
Номер
unknown, С. 4984 - 5001
Опубликована: Март 10, 2025
Unprecedented
chiral
ruthenium(II)
complexes
with
phthalocyanines
having
motifs
near
the
catalytic
metal
site
have
been
prepared
by
cross
condensation
of
3,6-bis-aryloxy-phthalonitrile
(α-Ar*O)2Pn
bearing
two
(1R,2S,5R)-menthoxy
groups
orthogonal
to
aromatic
plane
and
(15-crown-5)phthalonitrile.
Four
containing
menthyl
(M)
15-crown-5
units
(C),
notably
RuPc[MC3](CO),
RuPc[opp-M2C2](CO),
RuPc[adj-M2C2](CO),
RuPc[M3C](CO),
were
isolated
in
pure
form
fully
characterized
UV–vis,
circular
dichroism,
HRMS,
various
1H
NMR
13C
techniques.
Their
evaluation
benchmark
asymmetric
cyclopropanation
reaction
styrene
derivatives
ethyl
diazoacetate
indicated
that
RuPc[opp-M2C2](CO)
complex
was
most
efficient
terms
diastereo-
enantioselectivity.
Further
study
revealed
strong
dependence
stereoselectivity
on
solvent
nature
salt
additives,
which
caused
conformational
rearrangement
flexible
surrounding,
as
evidenced
multinuclear
CD
spectra.
For
instance,
upon
moving
from
commonly
used
CH2Cl2
EtOH
addition
NaPF6,
a
significant
enhancement
enantioselectivity
(from
35
84%
p-methylstyrene)
obtained.
Of
particular
importance
is
very
high
diastereoselectivity
many
substrates
promoted
incorporation
sodium
cations
into
crown
ether
cavities
phthalocyanine
attain
trans/cis
ratio
up
499:1.
Such
regulating
effect
catalysis
involving
tetrapyrrolic
has
not
previously
observed,
rendering
this
prominent
example
tunable
catalyst.
The
developed
synthetic
strategy
paves
way
environment
around
receptors
tune
properties.
Язык: Английский
Enantioselective Alkylation of Primary C(sp3)–H Bonds in N-Methyl Tertiary Amine Enabled by Iridium Complex of Axially Chiral β-Aryl Porphyrins
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 27, 2024
A
fine-tuning
of
enantioselective
carbene
insertion
into
primary
C(
Язык: Английский