Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(44)
Published: Sept. 1, 2023
Utilization
of
oxime
ethers
as
bifunctional
reagents
remains
unknown.
Herein,
we
present
a
mechanistically
distinct
strategy
that
enables
oximesulfonylation
olefins
using
sulfonyl-oxime-ethers
under
metal-free
photochemical
conditions.
Via
concomitant
C-S
and
C-C
bond
formation,
the
process
permits
incorporation
sulfonyl
groups
into
in
complete
atom-economic
fashion,
providing
rapid
access
to
multi-functionalized
β-sulfonyl
with
good
yields
stereoselectivity.
The
method
is
amenable
functionalization
complex
bioactive
molecules
shown
be
scalable.
A
radical
chain
mechanism
initiated
via
Hydrogen
Atom
Transfer
(HAT)
mediated
N-O
cleavage
suggested
for
process,
based
on
our
results
mechanistic
investigations.
Advanced Synthesis & Catalysis,
Journal Year:
2024,
Volume and Issue:
366(16), P. 3430 - 3437
Published: April 10, 2024
Abstract
In
this
manuscript
a
general
photocatalytic
approach
for
the
synthesis
of
alkyl‐substituted
gem
‐difluoroalkenes
using
readily
available
oxime
esters
and
1‐bromo‐1,1‐difluoroprop‐2‐ene
(BDFP)
has
been
established.
This
strategy
involving
radical
bromo
elimination
provides
access
to
large
variety
value‐added
fluorinated
molecules.
The
mild
reaction
conditions
are
compatible
with
many
functional
groups
including
complex
natural
products
or
drug
Experimental
theoretical
mechanistic
investigations
indicate
that
efficiency
process
relies
on
crucial
role
imine
radical,
which
is
formed
after
photoexcitation
via
energy
transfert
(EnT)
decarboxylation
ester.
Indeed,
would
either
behave
as
bromine
scavenger
an
XAT
promoter
in
reaction.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 19, 2024
C–P
bond
formation
has
typically
been
achieved
by
a
single-electron
transfer
process.
Herein,
novel
class
of
oxime
ester
bifunctionalization
reagents
were
first
applied
to
the
photocatalytic
β-aminophosphorylation
modular
olefins.
The
bifunctional
generate
two
distinct
radical
species
(imine
and
phosphoryl
radicals)
that
exhibit
excellent
regioselectivity.
Subsequently,
these
radicals
are
attached
olefins
through
single-step
EnT
catalytic
process,
establishing
synthetic
pathway.
This
protocol
is
characterized
regioselectivity,
broad
functional
group
tolerance,
mild
reaction
conditions,
which
would
enrich
diversity
versatility
facilitate
diversity-oriented
synthesis
β-aminophosphorylated
complex
molecule
scaffolds.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(44)
Published: Sept. 1, 2023
Utilization
of
oxime
ethers
as
bifunctional
reagents
remains
unknown.
Herein,
we
present
a
mechanistically
distinct
strategy
that
enables
oximesulfonylation
olefins
using
sulfonyl-oxime-ethers
under
metal-free
photochemical
conditions.
Via
concomitant
C-S
and
C-C
bond
formation,
the
process
permits
incorporation
sulfonyl
groups
into
in
complete
atom-economic
fashion,
providing
rapid
access
to
multi-functionalized
β-sulfonyl
with
good
yields
stereoselectivity.
The
method
is
amenable
functionalization
complex
bioactive
molecules
shown
be
scalable.
A
radical
chain
mechanism
initiated
via
Hydrogen
Atom
Transfer
(HAT)
mediated
N-O
cleavage
suggested
for
process,
based
on
our
results
mechanistic
investigations.
