Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Sept. 12, 2024
Enantioenriched
unnatural
amino
acids
represent
a
prevalent
motif
in
organic
chemistry,
with
profound
applications
biochemistry,
medicinal
and
materials
science.
Herein,
we
report
cobalt-catalyzed
aza-Barbier
reaction
of
dehydroglycines
unactivated
alkyl
halides
to
afford
α-amino
esters
high
enantioselectivity.
This
catalytic
reductive
alkylative
addition
protocol
circumvents
the
use
moisture-,
air-sensitive
organometallic
reagents,
stoichiometric
chiral
auxiliaries,
enabling
conversion
variety
primary,
secondary,
even
tertiary
α-alkyl-amino
under
mild
conditions,
thus
leading
broad
functional
group
tolerance.
The
expedient
access
biologically
active
motifs
demonstrates
practicality
this
by
reducing
number
synthetic
steps
enhancing
efficiency.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(51)
Published: Nov. 3, 2023
Bicyclo[3.2.1]octadiene
compounds
and
derivatives
exist
in
a
number
of
natural
products
bioactive
compounds.
Nevertheless,
catalytic
enantioselective
protocols
for
the
synthesis
these
skeletons
have
not
been
disclosed.
Herein
we
reported
palladium-catalyzed
asymmetric
intramolecular
alkene-alkyne
coupling
alkyne-tethered
cyclopentenes,
affording
library
enantionenriched
bicyclo[3.2.1]octadienes
excellent
yields
enantioselectivities
(mostly
>99
%
ee).
Moreover,
could
undergo
an
unusual
iodination-induced
1,2-acyl
migration,
forming
iodinated
with
three
vicinal
stereocenters.
The
enone
isolated
olefin
motifs
embedded
provide
useful
handles
downstream
elaboration.
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 12, 2025
This
study
explores
the
roles
of
halide
ligands
and
external
electric
fields
(EEFs)
in
tuning
reactivity
cobalt-catalyzed
oxidative
cyclometalation
(OCM)
1,6-enynes,
focusing
on
concerted
mechanism.
Using
density
functional
theory
(DFT),
we
investigate
how
these
factors
influence
key
processes
OCM
step,
particularly
cleavage
π
bonds,
formation
M-C
creation
a
new
C-C
bond.
Our
findings
show
that
polar
solvents
lower
activation
barriers,
while
increase
them,
inhibiting
reaction
by
weakening
back-donation
reducing
orbital
overlap.
However,
strategic
application
EEFs
counteracts
this
inhibition,
enhancing
electron
back-donation,
stabilizing
transition
state,
facilitating
bond
formation.
The
Dewar-Chatt-Duncanson
(DCD)
model,
distortion/interaction
analysis,
quantum
atoms
molecules
(QTAIM)
delocalization
index
(DI)
calculation
reveal
reduce
cobalt
center,
π-back-donation
raising
energy
barriers.
work
provides
insights
into
electronic
geometric
can
be
manipulated
to
optimize
catalytic
performance
synthetic
transformations.
Chemical Science,
Journal Year:
2022,
Volume and Issue:
14(5), P. 1123 - 1131
Published: Dec. 21, 2022
A
highly
enantioselective
palladium-catalyzed
hydrosilylation
of
1,3-diynes
with
dihydrosilanes
was
established
for
the
facile
preparation
Si-stereogenic
enynes
and
an
enyne-linked
chiral
polymer
(polyenyne)
in
good
yields
excellent
ees.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(23), P. 4359 - 4365
Published: June 7, 2023
A
highly
regio-
and
stereoselective
hydrochlorination/cyclization
of
enynes
has
been
reported
by
FeCl3
catalysis.
variety
undergo
this
cyclization
transformation
with
acetic
chloride
as
the
chlorine
source
H2O
providing
protons
via
a
cationic
pathway.
This
protocol
provides
cheap,
simple,
stereospecific,
effective
to
afford
heterocyclic
alkenyl
compounds
Z
isomers
high
yields
(≤98%)
regioselectivity.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Sept. 12, 2024
Enantioenriched
unnatural
amino
acids
represent
a
prevalent
motif
in
organic
chemistry,
with
profound
applications
biochemistry,
medicinal
and
materials
science.
Herein,
we
report
cobalt-catalyzed
aza-Barbier
reaction
of
dehydroglycines
unactivated
alkyl
halides
to
afford
α-amino
esters
high
enantioselectivity.
This
catalytic
reductive
alkylative
addition
protocol
circumvents
the
use
moisture-,
air-sensitive
organometallic
reagents,
stoichiometric
chiral
auxiliaries,
enabling
conversion
variety
primary,
secondary,
even
tertiary
α-alkyl-amino
under
mild
conditions,
thus
leading
broad
functional
group
tolerance.
The
expedient
access
biologically
active
motifs
demonstrates
practicality
this
by
reducing
number
synthetic
steps
enhancing
efficiency.
