Catalyst-Controlled Regiodivergence in Rearrangements of Indole-Based Onium Ylides
Published: Jan. 18, 2021
We
have
developed
catalyst-controlled
regiodivergent
rearrangements
of
onium-ylides
derived
from
indole
substrates.
Oxonium
ylides
formed
<i>in
situ</i>
substituted
indoles
selectively
undergo
[2,3]-
and
[1,2]-rearrangements
in
the
presence
a
rhodium
copper
catalyst,
respectively.
The
combined
experimental
density
functional
theory
(DFT)
computational
studies
indicate
divergent
mechanistic
pathways
involving
metal-free
ylide
catalyzed
reaction
favoring
[2,3]-rearrangement,
metal-coordinated
ion-pair
[1,2]-rearrangement
that
recombines
solvent-cage.
application<br>of
our
methodology
was
demonstrated
first
total
synthesis
alkaloid
(±)-sorazolon
B,
which
enabled
stereochemical
reassignment
natural
product.
Further
group
transformations
rearrangement
products
to
generate
valuable
synthetic
intermediates
were
also
demonstrated.
Language: Английский
Effects of Axial Solvent Coordination to Dirhodium Complexes on Reactivity and Selectivity in C–H Insertion Reactions: A Computational Study
Published: Nov. 16, 2021
Density
functional
theory
calculations
were
used
to
systematically
explore
the
effects
of
axial
ligation
by
solvent
molecules
on
reactivity
and
selectivity
dirhodium
tetracarboxylates
with
diazo
compounds
in
context
C–H
insertion
into
propane.
Insertions
three
types
compounds—acceptor/acceptor,
donor/acceptor,
donor/donor—promoted
tetraformate
tested
without
for
no
surrounding
solvent,
dichloromethane,
isopropanol,
acetonitrile.
Magnitudes,
origins,
consequences
structural
electronic
changes
arising
from
characterized.
The
results
suggest
that
affects
barriers
N2
extrusion
insertion,
former
a
larger
extent.
Language: Английский
Effects of Axial Solvent Coordination to Dirhodium Complexes on Reactivity and Selectivity in C–H Insertion Reactions: A Computational Study
Published: Oct. 8, 2021
Density
functional
theory
calculations
were
used
to
systematically
explore
the
effects
of
axial
ligation
by
solvent
molecules
on
reactivity
and
selectivity
dirhodium
tetracarboxylates
with
diazo
compounds
in
context
C–H
insertion
into
propane.
Insertions
three
types
compounds—acceptor/acceptor,
donor/acceptor,
donor/donor—promoted
tetraformate
tested
without
for
no
surrounding
solvent,
dichloromethane,
isopropanol,
acetonitrile.
Magnitudes,
origins,
consequences
structural
electronic
changes
arising
from
characterized.
The
results
suggest
that
affects
barriers
N2
extrusion
insertion,
former
a
larger
extent.
Language: Английский
Modulating Escape Channels of Cycloheptatrienyl Rhodium Carbenes to Form Semibullvalene
Published: April 5, 2023
We
report
the
various
escape
channels
available
to
dirhodium
carbene
intermediates
from
cycloheptatrienyl
diazo
compounds
with
density
functional
theory.
An
intramolecular
cyclopropanation
would,
in
principle,
provide
a
new
route
semibullvalenes.
A
full
exploration
of
potential
energy
surface
reveals
that
methylating
carbon-7
suppresses
competing
β-hydride
migration
pathway
heptafulvene
products,
giving
semibullvalene
formation
reasonable
chance.
During
our
explorations,
we
additionally
discovered
unusual
spirononatriene,
spironorcaradiene,
and
metal-stabilized
9-barbaralyl
cation
structures
as
local
minima.
Language: Английский
Effects of Axial Solvent Coordination to Dirhodium Complexes on Reactivity and Selectivity in C–H Insertion Reactions: A Computational Study
Published: Oct. 8, 2021
Density
functional
theory
calculations
were
used
to
systematically
explore
the
effects
of
axial
ligation
by
solvent
molecules
on
reactivity
and
selectivity
dirhodium
tetracarboxylates
with
diazo
compounds
in
context
C–H
insertion
into
propane.
Insertions
three
types
compounds—acceptor/acceptor,
donor/acceptor,
donor/donor—promoted
tetraformate
tested
without
for
no
surrounding
solvent,
dichloromethane,
isopropanol,
acetonitrile.
Magnitudes,
origins,
consequences
structural
electronic
changes
arising
from
characterized.
The
results
suggest
that
affects
barriers
N2
extrusion
insertion,
former
a
larger
extent.
Language: Английский
Effects of Axial Solvent Coordination to Dirhodium Complexes on Reactivity and Selectivity in C–H Insertion Reactions: A Computational Study
Published: Nov. 16, 2021
Density
functional
theory
calculations
were
used
to
systematically
explore
the
effects
of
axial
ligation
by
solvent
molecules
on
reactivity
and
selectivity
dirhodium
tetracarboxylates
with
diazo
compounds
in
context
C–H
insertion
into
propane.
Insertions
three
types
compounds—acceptor/acceptor,
donor/acceptor,
donor/donor—promoted
tetraformate
tested
without
for
no
surrounding
solvent,
dichloromethane,
isopropanol,
acetonitrile.
Magnitudes,
origins,
consequences
structural
electronic
changes
arising
from
characterized.
The
results
suggest
that
affects
barriers
N2
extrusion
insertion,
former
a
larger
extent.
Language: Английский