Angewandte Chemie,
Год журнала:
2021,
Номер
133(28), С. 15399 - 15403
Опубликована: Апрель 30, 2021
Abstract
Pentafluorosulfanyl
chloride
(SF
5
Cl)
is
the
most
prevalent
reagent
for
incorporation
of
SF
group
into
organic
compounds.
However,
preparation
Cl
often
relies
on
hazardous
reagents
and
specialized
apparatus.
Herein,
we
described
a
safe
practical
synthesis
bench‐stable
easy‐to‐handle
solution
in
n
‐hexane
under
gas‐reagent‐free
conditions.
The
synthetic
application
was
demonstrated
through
unprecedented
reaction
with
diazo
chemoselective
hydro‐
chloropentafluorosulfanylations
α‐diazo
carbonyl
compounds
were
developed
presence
K
3
PO
4
or
copper
catalyst,
respectively.
These
reactions
provide
direct
efficient
access
to
various
α‐pentafluorosulfanyl
high
value
potential
applications.
Journal of the American Chemical Society,
Год журнала:
2021,
Номер
143(45), С. 18864 - 18870
Опубликована: Ноя. 8, 2021
Here
we
report
a
contractive
synthesis
of
multisubstituted
cyclobutanes
containing
multiple
stereocenters
from
readily
accessible
pyrrolidines
using
iodonitrene
chemistry.
Mediated
by
nitrogen
extrusion
process,
the
stereospecific
involves
radical
pathway.
Unprecedented
unsymmetrical
spirocyclobutanes
were
prepared
successfully,
and
concise,
formal
cytotoxic
natural
product
piperarborenine
B
is
reported.
Chemical Society Reviews,
Год журнала:
2022,
Номер
51(18), С. 8102 - 8139
Опубликована: Янв. 1, 2022
Hypervalent
iodine
compounds
as
environmentally
friendly
and
relatively
inexpensive
reagents
have
properties
similar
to
transition
metals.
They
are
employed
alternatives
metal
catalysts
in
organic
synthesis
mild,
nontoxic,
selective
recyclable
catalytic
reagents.
Formation
of
C-N,
C-O,
C-S,
C-F
C-C
bonds
can
be
seamlessly
accomplished
by
hypervalent
catalysed
oxidative
functionalisations.
The
aim
this
review
is
highlight
recent
developments
the
utilisation
iodine(III)
iodine(V)
a
wide
range
including
chiral
for
stereoselective
synthesis.
Polymer-,
magnetic
nanoparticle-
framework-supported
also
described.
Organic & Biomolecular Chemistry,
Год журнала:
2021,
Номер
19(5), С. 947 - 964
Опубликована: Янв. 1, 2021
This
review
will
cover
the
importance
of
and
most
recent
approaches
toward
geminal
difluoroalkyl
groups
using
transition
metal-mediated,
photochemical,
organocatalytic,
other
methods.
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
60(28), С. 15271 - 15275
Опубликована: Апрель 30, 2021
Abstract
Pentafluorosulfanyl
chloride
(SF
5
Cl)
is
the
most
prevalent
reagent
for
incorporation
of
SF
group
into
organic
compounds.
However,
preparation
Cl
often
relies
on
hazardous
reagents
and
specialized
apparatus.
Herein,
we
described
a
safe
practical
synthesis
bench‐stable
easy‐to‐handle
solution
in
n
‐hexane
under
gas‐reagent‐free
conditions.
The
synthetic
application
was
demonstrated
through
unprecedented
reaction
with
diazo
chemoselective
hydro‐
chloropentafluorosulfanylations
α‐diazo
carbonyl
compounds
were
developed
presence
K
3
PO
4
or
copper
catalyst,
respectively.
These
reactions
provide
direct
efficient
access
to
various
α‐pentafluorosulfanyl
high
value
potential
applications.
Chemical Science,
Год журнала:
2021,
Номер
12(32), С. 10686 - 10695
Опубликована: Янв. 1, 2021
Short
aliphatic
groups
are
prevalent
in
bioactive
small
molecules
and
play
an
essential
role
regulating
physicochemistry
molecular
recognition
phenomena.
Nature Chemistry,
Год журнала:
2023,
Номер
15(11), С. 1515 - 1522
Опубликована: Окт. 16, 2023
Fluorinated
small
molecules
are
prevalent
across
the
functional
small-molecule
spectrum,
but
scarcity
of
naturally
occurring
sources
creates
an
opportunity
for
creative
endeavour
in
developing
routes
to
access
these
important
materials.
Iodine(I)/iodine(III)
catalysis
has
proven
be
particularly
well-suited
this
task,
enabling
abundant
alkene
substrates
readily
intercepted
by
situ-generated
λ3-iodanes
and
processed
high-value
(di)fluorinated
products.
These
organocatalysis
paradigms
often
emulate
metal-based
processes
engaging
π
bond
and,
case
styrenes,
facilitating
fluorinative
phenonium-ion
rearrangements
generate
difluoromethylene
units.
Here
we
demonstrate
that
enynes
competent
proxies
thereby
mitigating
recurrent
need
aryl
substituents,
highly
versatile
homopropargylic
difluorides
generated
operationally
simple
manner.
The
scope
method
is
disclosed,
together
with
application
target
synthesis
(>30
examples,
up
>90%
yield).
Journal of the American Chemical Society,
Год журнала:
2020,
Номер
142(47), С. 20048 - 20057
Опубликована: Ноя. 16, 2020
1,1-Disubstituted
styrenes
with
internal
oxygen
and
nitrogen
nucleophiles
undergo
oxidative
fluorocyclization
reactions
in
situ
generated
chiral
iodine(III)-catalysts.
The
resulting
fluorinated
tetrahydrofurans
pyrrolidines
contain
a
tertiary
carbon–fluorine
stereocenter.
Application
of
new
1-naphthyllactic
acid-based
iodine(III)-catalyst
allows
the
control
stereocenters
up
to
96%
ee.
Density
functional
theory
calculations
are
performed
investigate
details
mechanism
factors
governing
stereoselectivity
reaction.
Nature Communications,
Год журнала:
2021,
Номер
12(1)
Опубликована: Июнь 25, 2021
Fluorination
using
chiral
catalytic
methods
could
result
in
a
direct
access
to
asymmetric
fluorine
chemistry.
However,
challenges
fluorinations,
especially
the
longstanding
stereochemical
existed
BF3·Et2O-based
have
not
yet
been
addressed.
Here
we
report
nucleophilic
fluorination
BF3·Et2O
as
reagent
presence
of
iodine
catalyst.
Various
fluorinated
oxazine
products
were
obtained
with
good
excellent
enantioselectivities
(up
>99%
ee)
and
diastereoselectivities
>20:1
dr).
Control
experiments
(the
desired
fluoro-oxazines
be
when
Py·HF
or
Et3N·3HF
employed
source)
indicated
that
acted
only
but
also
activating
for
activation
iodosylbenzene.
Journal of the American Chemical Society,
Год журнала:
2021,
Номер
143(4), С. 1745 - 1751
Опубликована: Янв. 22, 2021
Metal-free,
catalytic
enantioselective
intermolecular
oxyamination
of
alkenes
is
realized
by
use
organoiodine(I/III)
chemistry.
The
protocol
applicable
toward
aryl-
and
alkyl-substituted
with
high
enantioselectivity
electronically
controlled
regioselectivity.
oxyaminated
products
can
be
easily
deprotected
in
one
step
to
reveal
free
amino
alcohols
yields
without
loss
enantioselectivity.
A
key
our
success
the
discovery
a
virtually
unexplored
chemical
entity,
N-(fluorosulfonyl)carbamate,
as
bifunctional
N,O-nucleophile.
