Molecules,
Journal Year:
2024,
Volume and Issue:
29(21), P. 5090 - 5090
Published: Oct. 28, 2024
Carbon–carbon
bond
formation
represents
a
key
reaction
in
organic
synthesis,
resulting
paramount
importance
for
constructing
the
carbon
backbone
of
molecules.
However,
traditional
metal-based
catalysis,
despite
its
advantages,
often
struggles
with
issues
related
to
efficiency,
selectivity,
and
sustainability.
On
other
hand,
while
biocatalysis
offers
superior
selectivity
due
an
extraordinary
recognition
process
substrate,
scope
applicable
reactions
remains
somewhat
limited.
In
this
context,
Artificial
Metalloenzymes
(ArMs)
Metallo
Peptides
(MPs)
offer
promising
not
fully
explored
solution,
merging
two
fields
transition
metal
catalysis
biotransformations,
by
inserting
catalytically
active
cofactor
into
customizable
protein
scaffold
or
coordinating
ion
directly
short
tunable
amino
acid
(Aa)
sequence,
respectively.
As
result,
these
hybrid
catalysts
have
gained
attention
as
valuable
tools
challenging
catalytic
transformations,
providing
systems
new-to-nature
properties
synthesis.
This
review
overview
recent
advances
development
ArMs
MPs,
focusing
on
their
application
asymmetric
carbon–carbon
bond-forming
reactions,
such
carbene
insertion,
Michael
additions,
Friedel–Crafts
cross-coupling
cyclopropanation,
underscoring
versatility
synthesizing
biologically
relevant
compounds.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(49)
Published: Aug. 13, 2024
Abstract
The
fluorinated
alcohols,
(CF
3
)
COH
(R
F9
OH)
and
2
MeCOH
F6
OH),
react
with
W(NR)
Cy
(Cy=Cyclohexyl;
R=2,6‐diisopropylphenyl
or
1‐adamantyl)
in
C
6
D
at
55
°C
to
give
cyclohexylidene
complexes.
Traditional
routes
terminal
alkylidene
complexes
(neopentylidene
neophylidene)
have
used
either
triflic
acid
HCl
(rarely),
but
relatively
weak
acids
are
sufficient
active
bisalkoxide
catalysts
therefore
prepared
directly.
An
α
hydrogen
abstraction
reaction
a
complex
from
biscyclohexyl
appears
be
as
facile
neopentylidene
neophylidene
ligand,
isomerization
of
cyclohexene
formed
through
β
is
also
possibility.
OR
ligands
can
replaced
readily
dimethylpyrrolide
(Me
Pyr)
other
more
basic
alkoxides.
Single
crystal
X‐ray
studies
were
carried
out
on
W(NAr)
,
W(NAr)(OR
(C
H
10
)(ArNH
),
W(NAd)(OR
)(AdNH
W(NAr)(O‐
i
‐Pr
Cy,
W(NAd)(η
1
‐Me
=cyclohexylidene).
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
unknown, P. 18204 - 18215
Published: Nov. 25, 2024
While
alkenylborons
have
emerged
as
powerful
precursors
for
the
stereospecific
construction
of
substituted
alkenes,
efficient
synthetic
methods
toward
stereodefined
trisubstituted
remain
limited.
Herein,
we
report
a
modular
and
practical
approach
stereoselective
synthesis
E-trisubstituted
through
nickel-catalyzed
three-component
reductive
coupling
two
readily
available
carbon
electrophiles
with
an
ethynyl-Bdan
reagent.
The
protocol
exhibits
broad
substrate
scope
good
functional
group
tolerance,
providing
expedient
access
to
variety
exclusive
E-selectivity.
work
demonstrates
possibility
applying
type
boron
reagent
in
organic
synthesis.
Molecules,
Journal Year:
2024,
Volume and Issue:
29(13), P. 3178 - 3178
Published: July 3, 2024
Catalyzed
by
Rh2(esp)2
(10
mol%)
and
(±)-BINAP
(20
in
DCE
at
80
°C,
the
cascade
assembly
between
diazobarbiturates
alkylidene
pyrazolones
proceeded
readily
produced
spiro-furopyrimidines
38–96%
chemical
yields.
The
structure
of
prepared
spirofuro-pyrimidines
was
firmly
confirmed
X-ray
diffraction
analysis.
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(49)
Published: Aug. 13, 2024
Abstract
The
fluorinated
alcohols,
(CF
3
)
COH
(R
F9
OH)
and
2
MeCOH
F6
OH),
react
with
W(NR)
Cy
(Cy=Cyclohexyl;
R=2,6‐diisopropylphenyl
or
1‐adamantyl)
in
C
6
D
at
55
°C
to
give
cyclohexylidene
complexes.
Traditional
routes
terminal
alkylidene
complexes
(neopentylidene
neophylidene)
have
used
either
triflic
acid
HCl
(rarely),
but
relatively
weak
acids
are
sufficient
active
bisalkoxide
catalysts
therefore
prepared
directly.
An
α
hydrogen
abstraction
reaction
a
complex
from
biscyclohexyl
appears
be
as
facile
neopentylidene
neophylidene
ligand,
isomerization
of
cyclohexene
formed
through
β
is
also
possibility.
OR
ligands
can
replaced
readily
dimethylpyrrolide
(Me
Pyr)
other
more
basic
alkoxides.
Single
crystal
X‐ray
studies
were
carried
out
on
W(NAr)
,
W(NAr)(OR
(C
H
10
)(ArNH
),
W(NAd)(OR
)(AdNH
W(NAr)(O‐
i
‐Pr
Cy,
W(NAd)(η
1
‐Me
=cyclohexylidene).
Molecules,
Journal Year:
2024,
Volume and Issue:
29(21), P. 5090 - 5090
Published: Oct. 28, 2024
Carbon–carbon
bond
formation
represents
a
key
reaction
in
organic
synthesis,
resulting
paramount
importance
for
constructing
the
carbon
backbone
of
molecules.
However,
traditional
metal-based
catalysis,
despite
its
advantages,
often
struggles
with
issues
related
to
efficiency,
selectivity,
and
sustainability.
On
other
hand,
while
biocatalysis
offers
superior
selectivity
due
an
extraordinary
recognition
process
substrate,
scope
applicable
reactions
remains
somewhat
limited.
In
this
context,
Artificial
Metalloenzymes
(ArMs)
Metallo
Peptides
(MPs)
offer
promising
not
fully
explored
solution,
merging
two
fields
transition
metal
catalysis
biotransformations,
by
inserting
catalytically
active
cofactor
into
customizable
protein
scaffold
or
coordinating
ion
directly
short
tunable
amino
acid
(Aa)
sequence,
respectively.
As
result,
these
hybrid
catalysts
have
gained
attention
as
valuable
tools
challenging
catalytic
transformations,
providing
systems
new-to-nature
properties
synthesis.
This
review
overview
recent
advances
development
ArMs
MPs,
focusing
on
their
application
asymmetric
carbon–carbon
bond-forming
reactions,
such
carbene
insertion,
Michael
additions,
Friedel–Crafts
cross-coupling
cyclopropanation,
underscoring
versatility
synthesizing
biologically
relevant
compounds.
