The Chemical Record,
Год журнала:
2023,
Номер
23(9)
Опубликована: Апрель 26, 2023
Abstract
Carbamoyl
fluorides,
fluoroformates,
and
their
analogues
are
a
class
of
important
compounds
have
been
evidenced
as
versatile
building
blocks
for
the
preparation
useful
molecules
in
organic
chemistry.
While
major
achievements
were
made
synthesis
carbamoyl
last
half
20
th
century,
an
increasing
number
reports
focused
on
using
O/S/Se=CF
2
species
or
equivalents
fluorocarbonylation
reagents
direct
construction
these
from
parent
heteroatom‐nucleophiles
recent
years.
This
review
mainly
summarizes
advances
typical
application
by
halide
exchanges
reactions
since
1980.
Journal of the American Chemical Society,
Год журнала:
2021,
Номер
143(35), С. 14089 - 14096
Опубликована: Авг. 26, 2021
A
nickel-catalyzed,
multicomponent
regio-
and
enantioselective
coupling
via
sequential
hydroformylation
carbonylation
from
readily
available
starting
materials
has
been
developed.
This
modular
hydrofunctionalization
strategy
enables
the
straightforward
reductive
hydrocarbonylation
of
a
broad
range
unactivated
alkenes
to
produce
wide
variety
unsymmetrical
dialkyl
ketones
bearing
functionalized
α-stereocenter,
including
enantioenriched
chiral
α-aryl
α-amino
ketones.
It
uses
bisoxazoline
as
ligand,
silane
reductant,
chloroformate
safe
CO
source,
racemic
secondary
benzyl
chloride
or
an
N-hydroxyphthalimide
(NHP)
ester
protected
acid
alkylation
reagent.
The
benign
nature
this
process
renders
method
suitable
for
late-stage
functionalization
complex
molecules.
Journal of the American Chemical Society,
Год журнала:
2021,
Номер
143(33), С. 12961 - 12967
Опубликована: Авг. 12, 2021
Catalytic
asymmetric
dicarbofunctionalization
of
tethered
alkenes
has
emerged
as
a
promising
tool
for
producing
chiral
cyclic
molecules;
however,
it
typically
relies
on
aryl-tethered
to
form
benzene-fused
compounds.
Herein,
we
report
an
enantioselective
cross-electrophile
divinylation
reaction
nonaromatic
substrates,
2-bromo-1,6-dienes.
The
approach
thus
offers
route
new
architectures,
which
are
key
structural
motifs
found
in
various
biologically
active
proceeds
under
mild
conditions,
and
the
use
t-Bu-pmrox
3,5-difluoro-pyrox
ligands
resulted
formation
divinylated
products
with
high
chemo-,
regio-,
enantioselectivity.
method
is
applicable
incorporation
hetero-
carbocycles
into
complex
molecules.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(27)
Опубликована: Апрель 26, 2022
The
activation
of
SF6
,
a
potent
greenhouse
gas,
under
metal-free
and
visible
light
conditions
is
reported.
Herein,
mechanistic
investigations
including
EPR
spectroscopy,
NMR
studies
cyclic
voltammetry
allowed
the
rational
design
new
fluorinating
reagent
which
was
synthesized
from
2-electron
with
commercially
available
TDAE.
This
SF5
-based
efficiently
employed
for
deoxyfluorination
CO2
fluorinative
desulfurization
CS2
allowing
formation
useful
fluorinated
amines.
Moreover,
first
time
we
demonstrated
that
our
could
afford
mild
generation
Cl-SF5
gas.
finding
exploited
chloro-pentafluorosulfanylation
alkynes
alkenes.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(26)
Опубликована: Март 14, 2022
The
construction
of
multi-stereocenters
by
a
transition
metal-catalyzed
cross-coupling
reaction
is
major
challenge.
catalytic
desymmetric
functionalization
unactivated
alkenes
remains
largely
unexplored.
Herein,
we
disclose
-a
dicarbofunctionalization
1,6-dienes
via
nickel-catalyzed
reductive
reaction.
leverage
the
underdeveloped
chiral
8-Quinox
enables
Ni-catalyzed
carbamoylalkylation
both
mono-
and
disubstituted
to
form
pyrrolidinone
bearing
two
nonadjacent
stereogenic
centers
in
high
enantio-
stereoselectivitives
with
broad
functional-group
tolerance.
synthetic
application
pyrrolidinones
allows
rapid
access
complex
fused-heterocycles.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(30), С. 13461 - 13467
Опубликована: Июль 25, 2022
Asymmetric
cross-electrophile
difunctionalization
of
tethered
alkenes
has
become
a
powerful
tool
for
the
production
chiral
cyclic
scaffolds;
however,
current
studies
all
focus
on
carbocyclization
reactions.
Herein,
we
report
an
N-cyclization-alkylation
reaction
and
thus
showcase
potential
heterocyclization
accessing
new
enantioenriched
architectures.
This
work
establishes
approach
enantioselective
aza-Heck
cyclization/cross-coupling
sequence,
which
remains
long-standing
unsolved
challenge
synthetic
community.
The
proceeds
with
primary,
secondary,
few
tertiary
alkyl
iodides,
use
newly
defined
ligands
gave
highly
pyrrolines
improved
molecular
diversity
under
mild
conditions.
presence
imine
functionality
allows
further
structural
variations.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(14), С. 8150 - 8162
Опубликована: Апрель 4, 2023
Difunctionalization
of
olefins
offers
an
attractive
approach
to
access
complex
chiral
structures.
Reported
herein
is
the
design
N-protected
O-allylhydroxyamines
as
bifunctional
that
undergo
catalytic
asymmetric
1,2-carboamidation
with
three
classes
(hetero)arenes
afford
amino
alcohols
via
C-H
activation.
The
C═C
bond
in
O-allylhydroxyamine
activated
by
intramolecular
electrophilic
amidating
moiety
well
a
migrating
directing
group.
carboamidation
reaction
pattern
depends
on
nature
(hetero)arene
reagent.
Simple
achiral
reacted
give
centrally
β-amino
excellent
enantioselectivity.
employment
axially
prochiral
or
racemic
heteroarenes
afforded
both
axial
and
central
chirality
enantio-
diastereoselectivity.
In
case
heteroarenes,
coupling
follows
kinetic
resolution
s-factor
up
>600.
A
nitrene-based
mechanism
has
been
suggested
based
experimental
studies,
unique
mode
induction
diastereoselectivity
proposed.
Applications
alcohol
products
have
demonstrated.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(20), С. 11012 - 11018
Опубликована: Май 12, 2023
A
BF3-catalyzed
atom-economical
fluorocarbamoylation
reaction
of
alkyne-tethered
carbamoyl
fluorides
is
reported.
The
catalyst
acts
as
both
a
fluoride
source
and
Lewis
acid
activator,
thereby
enabling
the
formal
insertion
alkynes
into
strong
C-F
bonds
through
halide
recycling
mechanism.
developed
method
provides
access
to
3-(fluoromethylene)
oxindoles
γ-lactams
with
excellent
stereoselectivity,
including
fluorinated
derivatives
known
protein
kinase
inhibitors.
Experimental
computational
studies
support
stepwise
mechanism
for
involving
turnover-limiting
cyclization
step,
followed
by
internal
transfer
from
BF3-coordinated
adduct.
For
methylene
oxindoles,
thermodynamically
driven
Z-E
isomerization
facilitated
transition
state
aromatic
character.
In
contrast,
this
stabilization
not
relevant
γ-lactams,
which
results
in
higher
barrier
exclusive
formation
Z-isomer.
Synthesis,
Год журнала:
2023,
Номер
56(01), С. 1 - 15
Опубликована: Июнь 12, 2023
Abstract
Catalytic
enantioselective
1,2-dicarbofunctionalization
(1,2-DCF)
of
alkenes
is
a
powerful
transformation
growing
importance
in
organic
synthesis
for
constructing
chiral
building
blocks,
bioactive
molecules,
and
agrochemicals.
Both
two-
three-component
context,
this
family
reactions
generates
densely
functionalized,
structurally
complex
products
single
step.
Across
several
distinct
mechanistic
pathways
at
play
these
transformations
with
nickel
or
palladium
catalysts,
stereocontrol
can
be
obtained
through
tailored
ligands.
In
Review
we
discuss
the
various
strategies,
mechanisms,
catalysts
that
have
been
applied
to
achieve
enantioinduction
alkene
1,2-DCF.
1
Introduction
2
Two-Component
Enantioselective
1,2-DCF
via
Migratory
Insertion
3
Radical
Capture
4
Three-Component
5
6
Miscellaneous
Mechanisms
7
Conclusion
ACS Catalysis,
Год журнала:
2021,
Номер
11(21), С. 13217 - 13222
Опубликована: Окт. 15, 2021
A
mild
visible-light-induced
Pd-catalyzed
one-pot
three-component
alkyl-carbamoylation
and
cyanation
of
alkenes
was
developed.
This
general
transformation,
which
proceeds
via
the
in
situ
formation
a
reactive
ketenimine
intermediate,
allows
for
rapid
construction
broad
range
valuable
amides
nitriles
from
readily
available
alkenes,
alkyl
iodides,
isocyanides.
An
efficient
synthesis
tetrazole
amidine
this
approach
also
demonstrated.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(36)
Опубликована: Июль 12, 2022
Herein,
we
leverage
the
Ni-catalyzed
enantioselective
reductive
dicarbofunctionalization
of
internal
alkenes
with
alkyl
iodides
to
enable
synthesis
chiral
pyrrolidinones
bearing
vicinal
stereogenic
centers.
The
application
newly
developed