Angewandte Chemie International Edition,
Год журнала:
2019,
Номер
58(36), С. 12486 - 12490
Опубликована: Июль 11, 2019
Abstract
A
catalytic,
enantio‐,
and
diastereoselective
formation
of
sulfenyl
acetals
bearing
multiple
stereogenic
centers
is
reported.
Alkenyl
aldehydes
undergo
a
chiral
thiiranium
ion
initiated
cascade
starting
with
intramolecular
capture
by
formyl
group
termination
HFIP
solvent.
This
method
provides
one‐pot
synthesis
dihydropyran
1,3‐disubstituted
isochroman
in
good
to
excellent
yield
high
levels
diastereo‐
(up
>99:1
dr)
enantiocontrol
99:1
er).
Chemical Reviews,
Год журнала:
2022,
Номер
122(15), С. 12544 - 12747
Опубликована: Июль 17, 2022
1,1,1,3,3,3-Hexafluoroisopropanol
(HFIP)
is
a
polar,
strongly
hydrogen
bond-donating
solvent
that
has
found
numerous
uses
in
organic
synthesis
due
to
its
ability
stabilize
ionic
species,
transfer
protons,
and
engage
range
of
other
intermolecular
interactions.
The
use
this
exponentially
increased
the
past
decade
become
choice
some
areas,
such
as
C–H
functionalization
chemistry.
In
review,
following
brief
history
HFIP
an
overview
physical
properties,
literature
examples
reactions
using
or
additive
are
presented,
emphasizing
effect
each
reaction.
Natural Product Reports,
Год журнала:
2019,
Номер
37(2), С. 276 - 292
Опубликована: Сен. 13, 2019
The
enantioselective
formation
of
quaternary
carbon
stereocenters
in
complex
natural
product
synthesis
the
latest
six
years
is
reviewed,
with
particular
emphasis
on
analysis
stereochemical
model
each
transformation.
Organic Chemistry Frontiers,
Год журнала:
2023,
Номер
10(5), С. 1322 - 1345
Опубликована: Янв. 1, 2023
Functionalization
of
alkenes/alkynes
is
a
highly
effective
route
to
achieve
molecular
complexity.
This
review
summarizes
recent
progresses
on
the
1,2-difunctionalization/hydrofunctionalization
unactivated
with
C−S
bond
formation.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(10)
Опубликована: Янв. 17, 2024
Abstract
An
efficient
catalytic
asymmetric
electrophilic
sulfenylation
reaction
for
the
synthesis
of
planar‐chiral
sulfur‐containing
cyclophanes
has
been
developed
first
time.
This
was
achieved
by
using
a
new
Lewis
base
catalyst
and
ortho
‐trifluoromethyl‐substituted
sulfenylating
reagent.
Using
substrates
with
low
rotational
energy
barrier,
transformation
proceeded
through
dynamic
kinetic
resolution,
high
barrier
allowed
to
undergo
resolution
process.
Meanwhile,
this
compatible
desymmetrization
process
when
symmetric
were
used.
Various
readily
obtained
in
moderate
excellent
yields
enantioselectivities
(up
97
%
yield
95
ee).
approach
used
synthesize
pharmaceutically
relevant
molecules.
Density
functional
theory
calculations
showed
that
π‐π
interactions
between
sulfenyl
group
aromatic
ring
substrate
play
crucial
role
enantioinduction
reaction.
The Chemical Record,
Год журнала:
2019,
Номер
20(2), С. 142 - 161
Опубликована: Июль 2, 2019
Abstract
Fluorinated
alcohols
have
been
widely
used
in
the
synthetic
organic
chemistry
over
past
decades.
The
unique
properties
such
as
strong
hydrogen‐bonding
donor
ability
and
low
nucleophilicity
allow
them
to
promote
reactions
absence
of
any
catalyst.
These
approaches
distinct
advantages
terms
operational
simplicity,
practicability
environmental
friendliness.
Reactions
promoted
by
fluorinated
alcohols,
including
nucleophilic
substitution
reactions,
annulation
electrophilic
dearomatization
functionalization
multiple
bond,
epoxidation
miscellaneous
summarized
this
account.
Angewandte Chemie International Edition,
Год журнала:
2018,
Номер
57(31), С. 9785 - 9789
Опубликована: Июнь 8, 2018
An
interrupted
Pummerer/nickel-catalysed
cross-coupling
strategy
has
been
developed
and
used
in
the
elaboration
of
styrenes.
The
operationally
simple
method
can
be
carried
out
as
a
one-pot
process,
involves
direct
formation
stable
alkenyl
sulfonium
salt
intermediates,
utilises
commercially
available
sulfoxide,
catalyst,
ligand,
operates
at
ambient
temperature,
accommodates
sp-,
sp2
-,
sp3
-hybridised
organozinc
coupling
partners,
delivers
functionalised
styrene
products
high
yields
over
two
steps.
Pummerer/cyclisation
approach
also
to
access
carbo-
heterocyclic
salts
for
cross-coupling.
Angewandte Chemie International Edition,
Год журнала:
2020,
Номер
59(12), С. 4959 - 4964
Опубликована: Янв. 22, 2020
The
enantioselective
construction
of
axially
chiral
compounds
by
electrophilic
carbothiolation
alkynes
is
disclosed
for
the
first
time.
This
transformation
enabled
use
a
Ts-protected
bifunctional
sulfide
catalyst
and
Ms-protected
ortho-alkynylaryl
amines
(Ts=tosyl;
Ms=mesyl).
Both
arylthiolating
trifluoromethylthiolating
reagents
are
suitable
this
reaction.
obtained
products
vinyl-aryl
amino
sulfides
can
be
easily
converted
into
biaryl
sulfides,
sulfoxides,
amines,
other
valuable
difunctionalized
compounds.
Journal of the American Chemical Society,
Год журнала:
2018,
Номер
140(46), С. 15621 - 15625
Опубликована: Ноя. 9, 2018
A
catalytic,
enantioselective
method
for
the
preparation
of
chiral,
non-racemic,
alkylboronic
esters
bearing
two
vicinal
stereogenic
centers
is
described.
The
reaction
proceeds
via
a
1,2-migration
zwitterionic
thiiranium–boronate
complex
to
give
exclusively
anti
carbosulfenylation
products.
broad
scope
aryl
groups
migrate
with
good
yield
and
excellent
enantioselectivity
(up
99:1
e.r.).
Similarly,
range
di-
trisubstituted
alkenylboronic
are
competent
partners.
This
provides
access
both
secondary
tertiary
chiral
esters.
Synthesis,
Год журнала:
2018,
Номер
51(01), С. 67 - 82
Опубликована: Ноя. 15, 2018
Cascade
polyene
cyclization
reactions
are
highly
efficient
and
elegant
bioinspired
transformations
that
involve
simultaneous
multiple
bond
constructions
to
rapidly
generate
complex
polycyclic
molecules.
This
review
summarizes
the
most
prominent
work
on
a
variety
of
cationic
radical
cascade
cyclizations
their
applications
in
natural
product
synthesis
published
between
2014
2018.
1
Introduction
2
Cationic
Polyene
Cyclizations
2.1
Lewis
Acid
Mediated
2.2
Brønsted
2.3
Halogen
Electrophile
Initiated
2.4
Sulfur
2.5
Transition-Metal-Mediated
3
Radical
3.1
3.2
Photocatalyst-Mediated
4
Origin
Stereocontrol
5
Conclusion
ACS Catalysis,
Год журнала:
2020,
Номер
10(18), С. 10794 - 10802
Опубликована: Авг. 26, 2020
Aniline
derivatives
are
frequently
encountered
in
molecules
of
industrial
relevance
such
as
dyes
or
antioxidants,
which
make
the
development
synthetic
methods
for
functionalization
these
privileged
structures
highly
sought-after.
A
general
protocol
hydroarylation
electronically
diverse
alkenes
with
anilines
would
be
ideal
to
provide
densely
functionalized
compounds.
However,
this
transformation
has
been
underexplored
compared
more
traditional
unactivated
because
significant
challenges
associated
control
selectivity
and
its
substrate
tolerance.
Herein,
we
describe
a
selective,
versatile,
user-friendly
ortho-C-alkylation
that
hinges
on
beneficial
combination
Lewis
acid
(Ca(II))
hexafluoroisopropanol
solvent.
This
allows
extension
deactivated
styrenes
demonstrates
remarkable
improved
reactivity
regarding
aliphatic
alkenes,
styrene
derivatives,
dienes.
In
addition,
DFT
computations
were
performed
which,
combined
experimental
observations,
suggest
nearly
concerted
mechanism
impart
ortho-selectivity.
