Organic Letters,
Год журнала:
2022,
Номер
24(47), С. 8603 - 8608
Опубликована: Ноя. 20, 2022
A
chiral
Lewis
base
catalyzed
enantioselective
N-allylic
alkylation
of
2-hydroxypyridines
and
MBH
carbonates
is
documented,
affording
a
convenient
access
to
N-alkylated
2-pyridones
with
up
99%
ee
yield.
Experimental
computational
studies
have
revealed
that
the
strong
hydrogen
bond
interaction
between
catalyst
plays
crucial
role
in
this
reaction
for
reactivity,
chemoselectivity,
enantioselectivity.
The
rare
[1,2]-sigmatropic
rearrangement
of
sulfoxonium-iodonium
hybrid
ylides
is
described,
which
enables
the
efficient
sulfoxidation/sulfonylation-alkylation
I(III)/S(VI)
with
1,3-dicarbonyls.
By
slight
modification
reaction
conditions,
controllable
alkylation-hydroxylation
and
dialkylation
were
achieved.
This
strategy
affords
a
diverse
array
α,α-difunctionalized
ketones
in
moderate
to
good
yields,
demonstrating
broad
substrate
scope.
These
findings
provide
an
important
advancement
sulfoxonium
highlight
divergent
reactivity
ylides.
Chemistry - An Asian Journal,
Год журнала:
2023,
Номер
18(10)
Опубликована: Апрель 8, 2023
Abstract
A
novel
and
facile
method
for
the
synthesis
of
N
‐β‐CF
3
‐substituted
2‐pyridones
via
hydroamination
α‐(trifluoromethyl)styrenes
with
was
described.
The
reaction
proceeded
smoothly
at
room
temperature,
affording
a
variety
‐(β‐trifluoromethyl‐β‐arylethyl)pyridin‐2(1
H
)‐ones
in
moderate
to
good
yields
excellent
‐regioselectivity.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(47)
Опубликована: Окт. 11, 2023
An
intermolecular
enantioselective
N-alkylation
reaction
of
1H-indoles
has
been
developed
by
cooperative
rhodium
and
chiral
phosphoric
acid
catalyzed
N-H
bond
insertion
reaction.
N-Alkyl
indoles
with
newly
formed
stereocenter
adjacent
to
the
indole
nitrogen
atom
are
produced
in
good
yields
(up
95
%)
excellent
enantioselectivities
>99
%
ee).
Importantly,
both
α-aryl
α-alkyl
diazoacetates
tolerated,
which
is
extremely
rare
asymmetric
X-H
(X=N,
O,
S
et
al.)
C-H
reactions.
With
this
method,
only
0.1
mol
catalyst
2.5
required
complete
conversion
as
well
achieve
high
enantioselectivity.
Computational
studies
reveal
relay
acid,
origin
chemo
stereoselectivity.
Organic Letters,
Год журнала:
2022,
Номер
24(47), С. 8603 - 8608
Опубликована: Ноя. 20, 2022
A
chiral
Lewis
base
catalyzed
enantioselective
N-allylic
alkylation
of
2-hydroxypyridines
and
MBH
carbonates
is
documented,
affording
a
convenient
access
to
N-alkylated
2-pyridones
with
up
99%
ee
yield.
Experimental
computational
studies
have
revealed
that
the
strong
hydrogen
bond
interaction
between
catalyst
plays
crucial
role
in
this
reaction
for
reactivity,
chemoselectivity,
enantioselectivity.
