Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(11)
Published: Jan. 26, 2024
Abstract
In
contrast
with
the
well‐established
C(sp
2
)−SCF
3
cross‐coupling
to
forge
Ar−SCF
bond,
corresponding
enantioselective
coupling
of
readily
available
alkyl
electrophiles
chiral
bond
has
remained
largely
unexplored.
We
herein
disclose
a
copper‐catalyzed
radical
range
secondary/tertiary
benzyl
radicals
easily
(Me
4
N)SCF
reagent.
The
key
success
lies
in
utilization
phosphino‐oxazoline‐derived
anionic
N,N,P‐ligands
through
tuning
electronic
and
steric
effects
for
simultaneous
control
reaction
initiation
enantioselectivity.
This
strategy
can
successfully
realize
two
types
asymmetric
reactions,
including
enantioconvergent
racemic
halides
three‐component
1,2‐carbotrifluoromethylthiolation
arylated
alkenes
under
mild
conditions.
It
therefore
provides
highly
flexible
platform
rapid
assembly
an
array
enantioenriched
SCF
‐containing
molecules
interest
organic
synthesis
medicinal
chemistry.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(11)
Published: Jan. 26, 2024
Abstract
In
contrast
with
the
well‐established
C(sp
2
)−SCF
3
cross‐coupling
to
forge
Ar−SCF
bond,
corresponding
enantioselective
coupling
of
readily
available
alkyl
electrophiles
chiral
bond
has
remained
largely
unexplored.
We
herein
disclose
a
copper‐catalyzed
radical
range
secondary/tertiary
benzyl
radicals
easily
(Me
4
N)SCF
reagent.
The
key
success
lies
in
utilization
phosphino‐oxazoline‐derived
anionic
N,N,P‐ligands
through
tuning
electronic
and
steric
effects
for
simultaneous
control
reaction
initiation
enantioselectivity.
This
strategy
can
successfully
realize
two
types
asymmetric
reactions,
including
enantioconvergent
racemic
halides
three‐component
1,2‐carbotrifluoromethylthiolation
arylated
alkenes
under
mild
conditions.
It
therefore
provides
highly
flexible
platform
rapid
assembly
an
array
enantioenriched
SCF
‐containing
molecules
interest
organic
synthesis
medicinal
chemistry.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(10), P. 7553 - 7561
Published: May 1, 2024
Epoxides
are
privileged
and
valuable
electrophiles
frequently
utilized
as
versatile
building
blocks
in
synthetic
chemistry
to
prepare
diverse
alcohols
through
ring-opening
reactions.
However,
the
catalytic
stereoconvergent
cross-coupling
of
racemic
epoxides
with
electro-
or
nucleophiles
has
remained
a
persistent
challenge.
In
this
work,
we
present
mild
method
achieve
regio-
enantioselective
alkynylation
various
alkynes,
resulting
synthesis
β-chiral
homopropargyl
via
photoinduced
copper-based
system.
The
use
monofluoro-substituted
non-C2
symmetric
bisoxazoline
diphenylamine
ligand
played
pivotal
role
success
chemistry,
its
distinct
electronic
steric
effects
proving
crucial
enhancing
both
reactivity
stereoselectivity.
Mechanistic
studies
supported
idea
that
reaction
underwent
regioselective
nucleophilic
iodides,
followed
by
radical
alkynes.
Notably,
hydroxyl
group
generated
from
epoxide
may
play
an
auxiliary
achieving
high
enantioselectivity.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(52)
Published: Nov. 1, 2022
The
para-Claisen
rearrangement
of
aryl
1-propargyl
ethers
involves
two-step
[3,3]-sigmatropic
rearrangements
and
dearomatization
process,
which
has
high
activation
barriers
is
challenge.
Here
we
discovered
thermal
naphthyl
ethers,
it
enabled
the
formation
formal
para-C-H
propargylation
products
upon
rearomatization.
Chirality
transfer
occurred
if
optically
active
propargyl
were
employed,
leading
to
construction
aryl/propargyl-containing
stereogenic
centers.
Moreover,
catalytic
asymmetric
with
different
substitution
at
para-position
gave
access
benzocyclohexenones
bearing
all-carbon
quaternary
stereocenters.
reaction
was
accelerated
by
a
chiral
N,N'-dioxide/Co(OTf)2
complex
catalyst
achieve
yields
(up
98
%)
enantioselectivities
93
%
ee).
DFT
calculations
experimental
results
provided
important
clues
clarify
process
as
well
induction
remote
delivery.
Chinese Journal of Chemistry,
Journal Year:
2023,
Volume and Issue:
42(10), P. 1161 - 1174
Published: Dec. 22, 2023
Comprehensive
Summary
As
a
versatile
earth‐abundant
transition
metal,
Cu
has
long
been
widely
applied
in
the
C—C
and
C—X
bond
forming
reactions.
for
now,
low‐valent
Cu(I)
is
known
to
reduce
redox
active
electrophiles
via
an
SET
pathway
give
corresponding
radical
Cu(II)
species.
The
resulting
species
can
interact
with
out‐sphere
pathway,
affording
coupling
product.
Alternatively,
trap
through
inner‐sphere
process
generate
Cu(III)
then
realize
challenging
formations
due
facile
reductive
elimination
of
intermediate.
Although
copper
catalysis
arylations
various
nucleophiles,
copper‐catalyzed
enantioconvergent
nucleophilic
substitutions
racemic
alkyl
have
less
explored,
likely
difficulties
overcoming
reduction
potential
electrophiles,
side
reactions,
enantiomeric
control.
In
order
overcome
high
photo‐induced
strategy
developed
under
mild
conditions.
An
alternative
new
anionic
tridentate
ligands
also
reported
this
regard.
This
review
summarizes
recent
developments
by
nucleophiles
C—N,
C—C,
C—B,
C—P
C—O
their
brief
mechanistic
studies.
Key
Scientists
2016,
Fu
Peters
et
al
.
first
Cu‐catalyzed
enantiocovergent
C—N
tertiary
halides
N
‐hetereocycles,
opening
door
substitutions.
that
greatly
enhances
reducing
power
Cu(I).
cyanation
(decarboxylative)
borylation
were
successively
presented
Liu
Ito
2017
2018,
respectively.
Other
than
strategy,
2019
demonstrated
significantly
enhance
ability
cinchona‐based
chiral
utilized
series
Zhang
containing
oxazoline
binding
sites
2020.
2020,
Xiao
Lu
al.
deoxygenative
cyanation.
Later
2022,
Feng
guanidine
hybrid
ligands.
focuses
on
emerged
years.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Jan. 1, 2024
A
properly
designed
chiral
copper
complex
with
a
hybrid
tridentate
ligand
enables
photocatalytic
asymmetric
cyanoalkylalkynylation
of
olefins
using
cycloketone
oxime
esters
as
the
precursors.
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: May 23, 2025
Herein
copper-catalyzed
Markovnikov
protoborylation
of
unactivated
terminal
alkenes
was
achieved
through
the
employment
a
bulky
σ-donating
guanidine
ligand.
The
reaction
demonstrated
good
tolerance
to
diverse
functional
groups
and
remarkable
selectivity
for
branched
borylation
products
(86:14-97:3)
under
ambient
conditions,
which
enabled
synthesis
secondary
alkyl
boronates
in
grams
with
further
valuable
derivatizations.
Mechanistic
studies
suggested
boryl
insertion
C═C
bonds
via
Cu-guanidine
complex
ruled
out
possibility
diboration-protodeboronation
process.
Organic & Biomolecular Chemistry,
Journal Year:
2024,
Volume and Issue:
22(17), P. 3453 - 3458
Published: Jan. 1, 2024
A
HOTf
or
Fe(OTf)
3
-catalyzed
dehydrative
alkynylation
of
3-hydroxyisoindolinones
with
terminal
alkynes
was
developed,
which
represents
a
brand-new
procedure
for
the
synthesis
3-alkynylated
3,3-disubstituted
isoindolinones.
Organic Chemistry Frontiers,
Journal Year:
2023,
Volume and Issue:
10(11), P. 2734 - 2739
Published: Jan. 1, 2023
Enantioselective
formal
(3
+
2)
cyclization
of
cyclic
β-keto
esters
with
azonaphthalenes
to
synthesize
cyclopenta[
b
]indoles
in
good
yields
high
diastereo-
and
enantioselectivity
is
established
by
using
guanidine-amides
as
catalysts
under
mild
reaction
conditions.
Chemical Communications,
Journal Year:
2023,
Volume and Issue:
59(53), P. 8250 - 8253
Published: Jan. 1, 2023
Using
newly
designed
α-imino
amide
surrogates
and
azlactones
as
amphiphilic
reactants,
catalyzed
by
a
chiral
bifunctional
guanidine,
the
construction
of
3,4-diaminopyrrolidine-2,5-diones
their
derivatives
was
realized
via
formal
[3+2]-cyclization.
The
role
guanidine
multiple
hydrogen
bond
donor
demonstrated
DFT
calculations.
