Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(13), С. 2996 - 3000
Опубликована: Май 7, 2024
Abstract
An
Iridium(III)‐catalyzed
C−H
cyclization
of
N‐arylphthalazinones
with
α‐diazotized
Meldrum's
acid
afforded
tetracyclic
phthalazine
derivatives
a
carbonyl
group
in
98%
yield
only
30
min.
The
initial
formation
also
provided
access
to
powerful
building
block.
utility
this
method
is
emphasized
by
the
synthetic
transformation
into
series
potentially
bioactive
derivatives.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Авг. 28, 2024
Considering
the
indispensable
significance
and
utilities
of
meta-substituted
pyridines
in
medicinal,
chemical
as
well
materials
science,
a
direct
meta-selective
C-H
functionalization
is
paramount
importance,
but
such
reactions
remain
limited
highly
challenging.
In
general,
established
methods
for
meta
rely
on
utilization
tailored
electrophilic
reagents
to
realize
intrinsic
polarity
match.
Herein,
we
report
complementary
electrochemical
methodology;
diverse
nucleophilic
sulfinates
allow
meta-sulfonylation
through
redox-neutral
dearomatization-rearomatization
strategy
by
tandem
dearomative
cycloaddition/hydrogen-evolution
electrooxidative
sulfonation
resulting
oxazino-pyridines/acid-promoted
rearomatization
sequence.
Besides,
several
salient
features,
including
exclusive
regiocontrol,
remarkable
substrate/functional
group
compatibility,
scale-up
potential,
facile
late-stage
modification,
have
been
demonstrated,
which
further
contributes
practicality
adaptability
this
approach.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Апрель 2, 2024
Abstract
An
ideal
approach
for
the
construction
of
aryl
boron
compounds
is
to
selectively
replace
a
C–H
bond
in
arenes
with
C–B
bond,
and
controlling
regioselectivity
one
most
challenging
aspects
these
transformations.
Herein,
we
report
an
iridium-catalyzed
trialkoxysilane
protecting
group-assisted
regioselective
borylation
arenes,
including
derivatives
benzaldehydes,
acetophenones,
benzoic
acids,
benzyl
alcohols,
phenols,
silanes,
multi-functionalized
aromatic
rings
are
all
well
tolerated
gave
para
-
selective
products
short
time
without
requirement
inert
gases
atmosphere.
The
site-selective
can
be
adjustable
by
installing
developed
group
on
different
functional
groups
ring.
Importantly,
preparation
process
trialkoxychlorosilane
efficient
scalable.
Mechanistic
computational
studies
reveal
that
steric
hindrance
plays
key
role
dictating
-selectivity.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(28), С. 19160 - 19167
Опубликована: Июль 3, 2024
Boronic
acids
and
esters
are
highly
regarded
for
their
safety,
unique
reactivity,
versatility
in
synthesizing
a
wide
range
of
small
molecules,
bioconjugates,
materials.
They
not
exploited
biocatalytic
synthesis,
however,
because
enzymes
that
can
make,
break,
or
modify
carbon–boron
bonds
rare.
We
wish
to
combine
the
advantages
boronic
molecular
assembly
with
biocatalysis,
which
offers
potential
unsurpassed
selectivity
efficiency.
Here,
we
introduce
an
engineered
protoglobin
nitrene
transferase
catalyzes
new-to-nature
amination
using
hydroxylamine.
Initially
targeting
aryl
acids,
show
enzyme
produce
array
anilines
high
yields
total
turnover
numbers
(up
99%
yield
>4000
TTN),
water
boric
acid
as
only
byproducts.
also
demonstrate
is
effective
bench-stable
esters,
hydrolyze
situ
corresponding
acids.
Exploring
enzyme's
capacity
enantioselective
catalysis,
found
racemic
alkyl
ester
affords
enantioenriched
amine,
transformation
achieved
chemocatalysts.
The
formation
exclusively
unrearranged
product
during
radical
clock
reaction's
stereospecificity
support
two-electron
process
akin
1,2-metallate
shift
mechanism.
developed
enables
new
routes
chiral
amines.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
63(1)
Опубликована: Ноя. 8, 2023
The
carbon-to-silicon
switch
in
formation
of
bioactive
sila-heterocycles
with
a
silicon-stereogenic
center
has
garnered
significant
interest
drug
discovery.
However,
metal-catalyzed
synthesis
such
scaffolds
is
still
its
infancy.
Herein,
rhodium-catalyzed
enantioselective
formal
[4+1]
cyclization
benzyl
alcohols
and
benzaldimines
been
realized
by
difunctionalization
secondary
silane
reagent,
affording
chiral-at-silicon
cyclic
silyl
ethers
sila-isoindolines,
respectively.
Mechanistic
studies
reveal
dual
role
the
rhodium-hydride
catalyst.
coupling
system
proceeds
via
enantio-determining
dehydrogenative
OH
silylation
alcohol
or
hydrosilylation
imine
to
give
an
enantioenriched
ether
silazane
intermediate,
same
rhodium
catalyst
also
enables
subsequent
intramolecular
cyclative
C-H
directed
pendent
Si-H
group.
Experimental
DFT
have
conducted
explore
mechanism
bond
alcohol,
where
Si-O
reductive
elimination
from
Rh(III)
hydride
intermediate
established
as
enantiodetermining
step.
Chemical Society Reviews,
Год журнала:
2023,
Номер
53(1), С. 361 - 379
Опубликована: Дек. 12, 2023
This
review
focuses
on
the
low-valent
heavy
group
14
compounds
stabilized
by
N-heterocyclic
boryl
ligands
and
their
applications
in
activation
of
small
molecules
inert
chemical
bonds.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(23)
Опубликована: Март 28, 2024
Abstract
Bimetallic
compounds
containing
direct
metal‐group
13
element
bonds
have
been
shown
to
display
unprecedented
patterns
of
cooperative
reactivity
towards
small
molecules,
which
can
be
influenced
by
the
identity
group
element.
In
this
context,
we
present
here
a
systematic
appraisal
metallo‐ligands
type
[(NON)E]
−
(NON=4,5‐bis(2,6‐di
iso
propylanilido)‐2,7‐di‐tert‐butyl‐9,9‐dimethylxanthene)
for
E=Al,
Ga
and
In,
through
comparison
structural
spectroscopic
parameters
associated
with
trans
L
or
X
ligands
in
linear
d
10
complexes
types
LM{E(NON)}
XM′{E(NON)}.
These
studies
are
facilitated
convenient
syntheses
(from
In(I)
precursor,
InCp)
potassium
indyl
species
[{K(NON)In}⋅KCp]
n
(
1
)
[(18‐crown‐6)
2
K
Cp]
[(NON)In]
1′
),
lead
first
characterisation
Ag−In
Hg−E
(E=Al,
In)
covalent
bonds.
The
resulting
structural,
quantum
chemical
probes
Ag/Hg
consistent
markedly
stronger
σ‐donor
capabilities
aluminyl
ligand,
[(NON)Al]
,
over
its
gallium
indium
counterparts.
Synlett,
Год журнала:
2024,
Номер
35(08), С. 862 - 876
Опубликована: Янв. 15, 2024
Abstract
The
field
of
C–H
functionalization
chemistry
has
experienced
rapid
growth
in
the
past
twenty
years,
with
increasingly
powerful
applications
organic
synthesis.
Recognizing
potential
this
emerging
to
impact
drug
discovery,
a
dedicated
effort
was
established
our
laboratories
more
than
ten
years
ago,
goal
facilitating
application
chemistries
active
medicinal-chemistry
programs.
Our
approach
centered
around
strategy
late-stage
(LSF)
wherein
is
employed
systematic
and
targeted
manner
generate
high-value
analogues
from
advanced
leads.
To
successfully
realize
approach,
we
developed
broadly
useful
LSF
platforms
workflows
that
increased
success
rates
accelerated
access
new
derivatives.
strategy,
when
properly
applied,
enabled
synthesis
molecules
designed
address
specific
issues.
Several
case
studies
are
presented,
along
descriptions
group’s
workflows.
1
Introduction
2
Building
an
Chemistry
Toolbox
2.1
Borylation
2.2
Minisci
Platforms
2.3
Automated
Direct-Metalation
Platform
3
Workflow
4
Application
Case
Studies
4.1
BTK
Inhibitor
Program
4.2
GPR40
Agonist
5
Conclusions
