Design
and
development
of
novel
one-step
reactions
that
produce
nitrogen-containing
scaffolds
is
an
invaluable
area
chemistry
due
to
the
abundance
these
moieties
in
natural
products
biologically
active
molecules.
Discovering
methods
using
uncommon
substrates
rare
earth
metals
access
significant
present
a
challenge.
Over
course
my
doctoral
studies,
I
have
designed,
developed
optimized
by
rarely
known
afforded
important
scaffolds.
The
obtained
allow
otherwise
long-to-synthesize
molecules
expeditious
construction
Chemistry - A European Journal,
Год журнала:
2023,
Номер
29(20)
Опубликована: Янв. 5, 2023
A
chiral
phosphoric
acid-catalyzed
enantioselective
aza-Friedel-Crafts
reaction
of
5-aminopyrazole
derivatives
with
cyclic
ketimines
attached
to
a
neutral
functional
group
is
reported.
This
protocol
allows
the
formation
pyrazole-based
C2-quaternary
indolin-3-ones
high
enantioselectivities
and
regioselectivities.
Moreover,
gram-scale
synthesis
5-aminopyrazole-based
was
performed,
no
decrease
in
yield
enantioselectivity.
Organic Letters,
Год журнала:
2023,
Номер
25(10), С. 1711 - 1716
Опубликована: Март 9, 2023
Herein,
we
described
a
highly
regio-
and
enantioselective
Friedel–Crafts
alkylation
of
aniline
derivatives
with
in
situ
generated
ortho-quinone
methides
enabled
by
chiral
phosphoric
acid,
furnishing
wide
range
enantioenriched
triarylmethanes
bearing
three
similar
benzene
rings
high
yields
(up
to
98%)
excellent
stereoselectivities
98%
ee).
Furthermore,
the
large-scale
reactions
diversified
transformations
product
demonstrate
practicality
protocol.
Density
functional
theory
calculations
elucidate
origin
enantioselectivity.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(5), С. 1430 - 1436
Опубликована: Янв. 1, 2024
Herein,
the
synthesis
of
2-(3,3-difluoro-2-phenylindolin-2-yl)-1-phenylethan-1-one
scaffolds
through
asymmetric
Mannich
reactions
between
3,3-difluoro
cyclic
ketimines
and
simple
ketones
is
described.
Abstract
The
efficient
synthesis
of
chiral
2,2‐disubstituted
indolin‐3‐ones
is
great
importance
due
to
its
significant
synthetic
and
biological
applications.
However,
catalytic
enantioselective
methods
for
de
novo
such
heterocycles
remain
scarce.
Herein,
a
novel
cyclizative
rearrangement
readily
available
anilines
vicinal
diketones
the
one‐step
construction
enantioenriched
presented.
reaction
proceeds
through
self‐sorted
[3+2]
heteroannulation/regioselective
dehydration/1,2‐ester
shift
process.
Only
phosphoric
acid
employed
promote
entire
sequence
simplify
manipulation
this
protocol.
Various
common
aniline
derivatives
are
successfully
applied
asymmetric
as
1,3‐binuclephiles
first
time.
Remarkably,
observed
stereoselectivity
proposed
originate
from
an
amine‐directed
regio‐
ortho
‐Csp
2
‐H
addition
ketones.
A
range
transformations
resulting
products
demonstrated
well.
Abstract
This
review
introduces
the
synthetic
organic
chemical
value
of
α‐bromocarbonyl
compounds
with
tertiary
carbons.
compound
a
carbon
has
been
used
primarily
only
as
radical
initiator
in
atom
transfer
polymerization
(ATRP)
reactions.
However,
recent
development
photo‐radical
reactions
(around
2010),
research
on
use
alkyl
precursors
became
popular
2012).
As
more
examples
were
reported,
studied
not
radicals
but
also
for
their
applications
organometallic
and
ionic
That
is,
act
nucleophiles
well
electrophiles.
The
carbonyl
group
is
attractive
because
it
allows
skeleton
to
be
converted
after
reaction,
being
applied
total
synthesis.
In
our
survey
until
2022,
can
perform
full
range
necessary
synthesis,
including
multi‐component
reactions,
cross‐coupling,
substitution,
cyclization,
rearrangement,
stereospecific
asymmetric
α‐Bromocarbonyl
have
created
new
trend
alkylation,
which
then
had
limited
reaction
patterns
focuses
how
chemistry.
The Journal of Organic Chemistry,
Год журнала:
2022,
Номер
87(16), С. 11097 - 11111
Опубликована: Авг. 5, 2022
Herein,
a
mild,
metal-free,
robust
approach
for
synthesizing
valuable
and
sterically
demanding
unsymmetrical
3,3-disubstituted
2-oxindoles
via
reductive
cyclization
of
α-ketoamides
is
reported.
This
operationally
simple
protocol
initiated
by
silyl
cation
further
catalyzed
Brønsted
acid.
We
have
utilized
wide
range
arenes,
amines,
thiols
as
coupling
partners
with
various
α-ketoamides.
The
products
were
afforded
in
excellent
regioselectivity
good
functional
group
tolerance.
procedure
provides
easy
access
to
the
scaffolds
azonazine
its
derivatives
an
syn-diastereoselectivity
bearing
all-carbon
quaternary
stereocenters.
Organic Chemistry Frontiers,
Год журнала:
2023,
Номер
10(20), С. 5274 - 5283
Опубликована: Янв. 1, 2023
The
asymmetric
Friedel–Crafts
alkylation
of
3-bromo-3-substituted
oxindoles
with
arenes
and
heteroarenes
was
achieved
to
synthesize
enantioenriched
C3-arylated
oxindoles.
Organic Chemistry Frontiers,
Год журнала:
2023,
Номер
10(10), С. 2476 - 2481
Опубликована: Янв. 1, 2023
We
have
herein
reported
a
hexafluoroisopropanol-promoted
para
-selective
Friedel–Crafts
alkylation
of
arenes.
Preliminary
mechanistic
studies
revealed
that
the
intramolecular
hydrogen
bond
network
HFIP
was
key
factor
in
realizing
site-selectivity.
Organic Letters,
Год журнала:
2024,
Номер
26(15), С. 3086 - 3090
Опубликована: Апрель 9, 2024
An
organocatalytic
enantioselective
alkylation
of
α,α-disubstituted
aldehydes
with
3-bromooxindoles
is
reported.
Enantioenriched
oxindoles
vicinal
quaternary
stereocenters
are
accessed
by
an
asymmetric
conjugate
addition
process
branched
o-azaxylylene
intermediates
(indol-2-ones).
Key
to
the
success
highly
diastereo-
and
transformations
combined
use
a
triphenylsilyl-protected
β-amino
alcohol
catalyst
derived
from
spiropyrrolidine
scaffold
3,5-dinitrobenzoic
acid.
This
study
also
presents
rare
example
aldehyde
formation
consecutive
stereocenters.
Chemistry - A European Journal,
Год журнала:
2024,
Номер
30(34)
Опубликована: Апрель 16, 2024
Abstract
Here
we
report
B(C
6
F
5
)
3/
CPA‐catalyzed
enantioselective
aza‐Diels–Alder
reaction
of
3,3‐difluoro‐2‐Aryl‐3
H
‐indoles
with
unactivated
dienes
to
access
chiral
10,10‐difluoro‐tetrahydropyrido[1,2‐
a
]indoles.
This
protocol
allows
the
formation
pyrazole‐based
C2‐quaternary
indolin‐3‐ones
high
enantioselectivities
and
regioselectivities.
Moreover,
gram‐scale
synthesis
]indole
skeleton
was
successfully
achieved
without
any
reduction
in
both
yield
enantioselectivity.
