Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(46)
Published: Sept. 23, 2022
Abstract
The
introduction
of
fluorine‐containing
groups
into
organic
molecules
can
significantly
affect
their
physical
and
chemical
properties
has
long
been
used
as
an
effective
strategy
for
drug
discovery
development.
Consequently,
the
development
catalytic
asymmetric
methods
synthesis
heterocycles
is
highly
desirable
sought
after.
Herein,
we
describe
a
nickel‐catalyzed
defluorinative
cyclization
fluoroalkyl‐substituted
1,6‐enynes,
providing
expedient
access
to
synthetically
attractive
4‐fluorovinyl‐substituted
2‐pyrrolidones
in
good
yields
with
remarkable
high
levels
chemo‐,
regio‐,
enantioselectivities
(90–99
%
ee,>35
examples).
This
protocol
features
readily
available
starting
materials
excellent
functional
group
compatibility,
exhibits
complementary
regioselectivity.
utility
this
was
demonstrated
enantioselective
antiepileptic
Seletracetam.
Angewandte Chemie International Edition,
Journal Year:
2018,
Volume and Issue:
58(2), P. 390 - 402
Published: June 28, 2018
Abstract
The
activation
of
carbon–fluorine
(C−F)
bonds
is
an
important
topic
in
synthetic
organic
chemistry.
Metal‐mediated
and
‐catalyzed
elimination
β‐
or
α‐fluorine
proceeds
under
milder
conditions
than
oxidative
addition
to
C−F
bonds.
initiated
from
organometallic
intermediates
having
fluorine
substituents
on
carbon
atoms
β
α
metal
centers,
respectively.
Transformations
through
these
processes
(C−F
bond
cleavage),
which
are
typically
preceded
by
carbon–carbon
(or
carbon–heteroatom)
formation,
have
been
increasingly
developed
the
past
five
years
as
methods.
In
this
Minireview,
we
summarize
applications
transition‐metal‐mediated
chemistry
a
historical
perspective
with
early
studies
systematic
recent
studies.
Chemical Reviews,
Journal Year:
2020,
Volume and Issue:
120(15), P. 7348 - 7398
Published: June 29, 2020
Organoborons
have
emerged
as
versatile
building
blocks
in
organic
synthesis
to
achieve
molecular
diversity
and
carboxylic
acid
bioisosteres
with
broad
applicability
drug
discovery.
Traditionally,
these
compounds
are
prepared
by
the
substitution
of
Grignard/lithium
reagents
electrophilic
boron
species
Brown
hydroboration.
Recent
developments
provided
new
routes
for
efficient
preparation
organoborons
applying
reactions
using
chemical
feedstocks
leaving
groups.
As
compared
previous
methods
that
used
halides
(I,
Br,
Cl),
direct
borylation
less
reactive
C–Het
C–C
bonds
has
become
highly
important
get
efficiency
functional-group
compatibility.
This
Review
aims
provide
a
comprehensive
overview
this
topic,
including
(1)
C–F
bond
borylation,
(2)
C–O
(3)
C–S
(4)
C–N
(5)
borylation.
Considerable
attention
is
given
strategies
mechanisms
involved.
We
expect
will
inspire
chemists
discover
more
transformations
expand
field.
Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
121(21), P. 13238 - 13341
Published: Oct. 7, 2021
Organoboron
reagents
represent
a
unique
class
of
compounds
because
their
utility
in
modern
synthetic
organic
chemistry,
often
affording
unprecedented
reactivity.
The
transformation
the
carbon–boron
bond
into
carbon–X
(X
=
C,
N,
and
O)
stereocontrolled
fashion
has
become
invaluable
medicinal
agrochemistry,
natural
products
chemistry
as
well
materials
science.
Over
past
decade,
first-row
d-block
transition
metals
have
increasingly
widely
used
catalysts
for
formation
bond,
traditionally
catalyzed
by
expensive
precious
metals.
This
recent
focus
on
alternative
enabled
growth
fundamental
methods
organoboron
chemistry.
review
surveys
current
state-of-the-art
use
element-based
bonds.
ACS Catalysis,
Journal Year:
2020,
Volume and Issue:
10(19), P. 11578 - 11622
Published: Aug. 25, 2020
Organoboronates
represent
a
cornerstone
functional
group
in
modern
synthesis
owing
to
their
unique
reactivity
and
divergent
synthetic
capability.
Copper
catalysis
has
become
one
of
the
most
powerful
methods
stereoselectively
install
boron
across
diverse
π-systems.
Additionally,
this
method
affords
tremendous
versatility
enabled
by
difunctionalization
π-system
addition
an
electrophile.
This
review
covers
known
electrophiles
intercept
catalytic
intermediates
borylative
strategies
that
have
been
reported
up
end
May
2020.
Chemical Society Reviews,
Journal Year:
2020,
Volume and Issue:
49(24), P. 9197 - 9219
Published: Jan. 1, 2020
Halodifluoromethyl
and
trifluoromethyl-containing
compounds
can
act
various
rolesviaselective
cleavage
modes
to
access
more
valuable
fluorinated
or
nonfluorinated
molecules.
Chemical Science,
Journal Year:
2018,
Volume and Issue:
10(3), P. 809 - 814
Published: Nov. 7, 2018
Synthesis
of
functionalized
gem-difluoroalkenes
was
achieved
through
nickel-catalyzed
allylic
defluorinative
alkylation
trifluoromethyl
alkenes
with
reductive
decarboxylation
redox-active
esters.
Angewandte Chemie International Edition,
Journal Year:
2019,
Volume and Issue:
59(10), P. 4009 - 4016
Published: Dec. 18, 2019
Fluorinated
organoboranes
serve
as
versatile
synthetic
precursors
for
the
preparation
of
value-added
fluorinated
organic
compounds.
Recent
progress
has
been
mainly
focused
on
transition-metal
catalyzed
defluoroborylation.
Herein,
we
report
a
photocatalytic
defluoroborylation
platform
through
direct
B-H
activation
N-heterocyclic
carbene
boranes,
synergistic
merger
photoredox
catalyst
and
hydrogen
atom
transfer
catalyst.
This
atom-economic
operationally
simple
protocol
enabled
an
extremely
broad
scope
multifluorinated
substrates
including
polyfluoroarenes,
gem-difluoroalkenes,
trifluoromethylalkenes
in
highly
selective
fashion.
Intriguingly,
can
be
free,
regioselectivity
obtained
is
complementary
to
reported
transition-metal-catalysis
many
cases.
Angewandte Chemie International Edition,
Journal Year:
2018,
Volume and Issue:
57(46), P. 15227 - 15231
Published: Sept. 25, 2018
An
efficient
method
for
the
metal-free
deaminative
borylation
of
alkylamines,
using
bis(catecholato)diboron
as
boron
source,
to
directly
synthesize
various
alkyl
potassium
trifluoroborate
salts
is
introduced.
The
key
this
high
reactivity
utilization
pyridinium
salt
activated
with
a
catalytic
amount
bipyridine-type
Lewis
base
promoter.
This
transformation
shows
good
functional-group
compatibility
(e.g.,
it
unimpeded
by
presence
ketone,
indole,
internal
alkene,
or
unactivated
chloride)
and
can
serve
powerful
synthetic
tool
amine
groups
in
complex
compounds.
Mechanistic
experiments
computations
suggest
mechanism
which
B2
cat2
unit
intercepts
an
radical
generated
single-electron
transfer
(SET)
from
boron-based
reductant.
Chemical Communications,
Journal Year:
2019,
Volume and Issue:
55(90), P. 13486 - 13505
Published: Jan. 1, 2019
α-Trifluoromethylstyrene
derivatives
are
versatile
synthetic
intermediates
for
the
preparation
of
more
complex
fluorinated
compounds.
Much
attention
has
been
paid
to
these
compounds
by
organic
chemistry
community,
because
they
have
successfully
utilized
in
C-F
bond
activation
a
CF3
group,
mainly
including
anionic
SN2'-type
substitution,
cationic
SN1'-type
ipso-substitution
and
defluorinative
functionalization
with
transition
metals
or
photoredox
catalysts.
In
addition,
metal-catalyzed
cycloaddition
reactions
α-trifluoromethylstyrenes
developed
construction
cycloalkanes
cycloalkenes
containing
fluoro
trifluoromethyl
groups.
this
review,
we
systematically
summarized
synthesis
their
applications
chemistry,
mechanisms
were
also
discussed.
Chemical Society Reviews,
Journal Year:
2021,
Volume and Issue:
50(23), P. 13129 - 13188
Published: Jan. 1, 2021
We
provide
a
comprehensive
overview
of
transition
metal-catalysed
asymmetric
borylation
processes
to
construct
C–B,
C–C,
and
other
C–heteroatom
bonds
with
considerable
attention
devoted
the
reaction
modes
mechanisms
involved.
