Organometallics,
Journal Year:
2024,
Volume and Issue:
44(1), P. 115 - 127
Published: Dec. 26, 2024
Reactions
of
RhH{κ3-P,O,P-[xant(PiPr2)2]}
(xant(PiPr2)2
=
9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene)
with
2
equiv
tert-butylacetylene
and
phenylacetylene
lead
to
the
acetylide
derivatives
Rh(C≡CR){κ3-P,O,P-[xant(PiPr2)2]}
(R
tBu,
Ph).
The
C–C
triple
bond
these
compounds
undergoes
B–H
anti-addition
pinacolborane
(HBpin)
produce
Rh{(E)-C(Bpin)=CHR-Pro-Z}{κ3-P,O,P-[xant(PiPr2)2]}
Ph),
which
regenerate
in
presence
a
new
alkyne
molecule,
releasing
respective
(Z)-borylolefin.
Complex
Rh{(E)-C(Bpin)=CHPh-Pro-Z}{κ3-P,O,P-[xant(PiPr2)2]}
is
unstable
toluene.
Initially,
double
borylalkenyl
ligand
E
Z
isomerization
Rh{(Z)-C(Bpin)═CHPh-Pro-E}{κ3-P,O,P-[xant(PiPr2)2]},
subsequently
evolves
aryl
derivative
Rh{C6H4-2-[E-CH═CH(Bpin)]}{κ3-P,O,P-[xant(PiPr2)2]}.
latter
reacts
molecule
Rh(C≡CPh){κ3-P,O,P-[xant(PiPr2)2]}
(E)-borylolefin.
According
this
reactivity,
complex
an
effective
catalyst
precursor
for
hydroboration
terminal
alkynes
mixtures
(Z)-
(E)-borylolefins.
molar
ratio
between
isomers
depends
on
substituent
alkyne;
para-substituted
substituents
electron-withdrawing
groups
favor
Z-borylolefin.
Chemical Society Reviews,
Journal Year:
2024,
Volume and Issue:
53(14), P. 7566 - 7589
Published: Jan. 1, 2024
Metal-catalyzed
highly
Markovnikov-type
selective
hydrofunctionalization
of
terminal
alkynes
provides
a
straightforward
and
atom-economical
route
to
access
1,1-disubstituted
alkenes,
which
have
wide
range
applications
in
organic
synthesis.
However,
the
transformations
are
challenging
due
electronic
steric
effects
during
addition
process.
With
development
metal-catalyzed
synthesis,
different
metal
catalysts
been
developed
solve
this
challenge,
especially
for
platinum
group
catalysts.
In
perspective,
we
review
homogeneous
according
classified
element
types
as
well
reaction
mechanisms.
Future
avenues
investigation
also
presented
help
expand
exciting
field.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(22)
Published: March 28, 2024
Abstract
Configurationally‐defined
dienes
are
pervasive
across
the
bioactive
natural
product
spectrum,
where
they
typically
manifest
themselves
as
sorbic
acid‐based
fragments.
These
C
5
motifs
reflect
biosynthesis
algorithms
that
facilitate
their
construction.
To
complement
established
biosynthetic
paradigms,
a
chemical
platform
to
construction
of
stereochemically
defined,
functionalizable
by
light‐enabled
isomerization
has
been
devised.
Enabled
selective
energy
transfer
catalysis,
variety
substituted
β‐boryl
acid
derivatives
can
be
isomerized
in
regio‐
and
stereo‐selective
manner
(up
97
:
3).
Directionality
is
guided
stabilizing
n
O
→p
B
interaction
product:
this
constitutes
formal
anti
‐hydroboration
starting
alkyne.
This
operationally
simple
reaction
employs
low
catalyst
loadings
(1
mol
%)
complete
1
h.
X‐ray
analysis
supports
hypothesis
leads
chromophore
bifurcation:
provides
structural
foundation
for
transfer.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 23, 2025
A
1,1-hydroboration
of
alkynylgermanes
with
unique
trans-Ge/B
stereochemistry
under
transition-metal-free
conditions
is
reported.
Mechanistic
studies
suggest
that
a
pathway
involving
α-boration
followed
by
stepwise
1,2-Ge/H
shift
on
the
intermediate
structurally
lies
between
an
alkyne-Ge+
π
complex
and
typical
vinyl
cation.
The
resulting
Ge/B
bimetallic
modules,
along
Ge*/Ge/B
trimetallic
variant,
can
be
conveniently
transformed
into
trisubstituted
olefins
through
iterative
divergent
cross-coupling.
This
work
demonstrates
incorporating
metalloids
classical
organic
reactions
may
offer
unconventional
chemical
selectivity
efficient
synthetic
applications.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(6), P. 2236 - 2242
Published: Jan. 1, 2024
With
the
aid
of
directing
group
strategy,
an
approach
for
synthesis
alkenyl
and
1-naphthyl
boronates
with
stereo-
regioselectivity
via
ligand-controlled
Ni-catalyzed
trans
-hydroboration/carboboration
internal
alkynes
was
developed.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(11), P. 2180 - 2185
Published: March 11, 2024
We
have
developed
visible-light-induced
trans-hydroboration
of
diaryl
alkynes
via
direct
photoexcitation
in-situ-generated
diboron
complexes,
affording
previously
elusive
(E)-1,2-diaryl-vinylboronates
with
high
stereoselectivity.
Experimental,
spectroscopic,
and
theoretical
mechanistic
studies
revealed
that
the
triplet-state
borate
complex
facilitates
B–B
bond
cleavage
desired
C–B
formation.
This
methodology
does
not
require
any
catalyst
is
operationally
simple.
The
highly
borylated
1,2-diaryl
alkenes
[1-(2-borylphenyl)vinyl)boronates]
are
shown
to
be
useful
as
building
blocks.
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 6, 2025
Gem-hydrogenative
cycloisomerization
and
sigmatropic
rearrangement
reactions
of
propargyl
alcohol
derivatives
with
different
Ru(II)
catalysts
afforded
cyclopropanation,
cyclopentenylation,
cyclohexenylation,
enol
acetate,
respectively.
To
understand
the
mechanism
origin
product
selectivity,
density
functional
theory
calculations
were
performed.
Calculated
results
reveal
that
electron-abundant
neutral
active
catalyst
[Cp*RuCl]
facilitate
formation
a
Cl-
counterion-assisted
π-back
bonding
between
Ru
σ*
C-H,
which
decreases
energy
barrier
agostic
interaction
determining
cyclopropane
product.
Whereas,
this
enyne
electron-deficient
cationic
[CpRu(MeCN)]+
is
prone
to
cyclopentenylation
through
C-C
bond
1,2-H
shift,
because
beneficial
for
shift.
With
[CpRu(MeCN)]+,
bearing
methyl
ether
can
facilely
undergo
ligand
exchange
afford
ascribed
strong
Ru···O
O
(methyl
ether).
Conversely,
bulky
silyl
unfavorable
proceed
cyclohexenylation
due
steric
repulsion
ether.
The
derivative
attached
nucleophilic
substituent
favorable
experience
[2,3]-sigmatropic
rather
than
cycloisomerization,
electrophilic
ruthenium
carbene.
Nature Communications,
Journal Year:
2025,
Volume and Issue:
16(1)
Published: May 27, 2025
Abstract
The
hydroboration
of
alkynes
is
a
textbook
example
syn
-selective
concerted
addition
reaction,
while
trans
additions
borane
to
remain
be
developed.
We
herein
report
transition
metal-free
anti
-addition
pinacolborane
alkynes,
facilitated
by
the
counteranion
effect.
This
work
further
develops
Chan
alkyne
reduction
utilizing
instead
aluminohydride
reagents,
enabling
facile
synthesis
valuable
five-membered
boracycles
that
constitute
isosteric
alternatives
bioactive
butenolides
and
versatile
platform
for
abundant
downstream
transformations.
practical
method
distinguished
excellent
regioselectivity,
broad
substrate
scope,
high
compatibility
with
variety
functional
groups.
exploration
patterns
affords
not
only
stereo-complementary
approach
traditional
organic
synthesis,
but
also
mandates
new
perspective
on
noncanonical
-hydroboration
mechanism.
A
combination
control
experiments
computational
studies
at
DFT
level
theory
reveal
previously
unrecognized
role
HMDS
in
stepwise
intermolecular
hydrogen
transfer
process.
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(22)
Published: March 28, 2024
Abstract
Configurationally‐defined
dienes
are
pervasive
across
the
bioactive
natural
product
spectrum,
where
they
typically
manifest
themselves
as
sorbic
acid‐based
fragments.
These
C
5
motifs
reflect
biosynthesis
algorithms
that
facilitate
their
construction.
To
complement
established
biosynthetic
paradigms,
a
chemical
platform
to
construction
of
stereochemically
defined,
functionalizable
by
light‐enabled
isomerization
has
been
devised.
Enabled
selective
energy
transfer
catalysis,
variety
substituted
β‐boryl
acid
derivatives
can
be
isomerized
in
regio‐
and
stereo‐selective
manner
(up
97
:
3).
Directionality
is
guided
stabilizing
n
O
→p
B
interaction
product:
this
constitutes
formal
anti
‐hydroboration
starting
alkyne.
This
operationally
simple
reaction
employs
low
catalyst
loadings
(1
mol
%)
complete
1
h.
X‐ray
analysis
supports
hypothesis
leads
chromophore
bifurcation:
provides
structural
foundation
for
transfer.
Bulletin of the Chemical Society of Japan,
Journal Year:
2024,
Volume and Issue:
97(8)
Published: July 31, 2024
Abstract
Organic
photoreactions
have
received
much
attention
as
unique
tools
to
access
kinetically
and/or
thermodynamically
prohibited
products
in
the
ground
state.
These
been
based
mainly
on
using
elements
with
high
electronegativity
such
carbon
(C),
oxygen
(O),
nitrogen
(N),
halogens
(F,
Cl,
Br,
and
I)
well
transition
metals.
On
other
hand,
we
interested
characteristics
of
low
electronegativity,
boron
(B),
silicon
(Si),
tin
(Sn),
excited
state,
enabling
highly
reactive
selective
photoinduced
borylations,
silylations,
stannylations.
In
this
account,
highlight
our
latest
findings
concerning
diverse
organic
utilizing
B,
Si,
Sn
elements,
which
are
challenging
when
conventional
strategies.
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(50)
Published: Aug. 15, 2024
Abstract
Die
Verwendung
von
diarylsubstituierten
Vinylboronaten,
einer
Klasse
chemischer
Bausteine
mit
wohlbekanntem
synthetischem
Nutzen,
ist
hauptsächlich
durch
die
Schwierigkeiten
bei
ihrer
Herstellung
begrenzt.
Wir
stellen
hier
eine
bequeme
synthetische
Strategie
vor,
auf
goldkatalysierten
Hiyama‐Arylierung
(
Z
)‐β‐(Borylvinyl)silanen
basiert,
Hydroborierung
Silylalkinen
leicht
zugänglich
sind.
Durch
Ausnutzung
der
hoch
elektronegativen
Natur
des
Gold(III)‐Zwischenprodukts
(das
lichtunterstützte
Oxidation
Aryldiazoniumsalzen
ist)
wird
selektive
Aktivierung
Silylgruppe
in
Gegenwart
Boreinheit
erreicht.
Dies
eröffnet
einen
Weg
zur
selektiven
Synthese
Diaryl‐substituierten
Vinylboronaten.
Reaktion
weist
breiten
Substratbereich,
ausgezeichnete
Toleranz
gegenüber
funktionellen
Gruppen
und
perfekte
Chemoselektivität
auf.
experimentelle
Studien
Dichtefunktionaltheorie
(DFT)‐Berechnungen
konnten
wir
den
Mechanismus
aufklären.
Das
Potenzial
wurde
nachgeschaltete
Transformationen
demonstriert,
einfachen
zu
bifunktionellen
Phenanthrenen
Triaryl‐substituierten
Olefinen
bieten.
