Angewandte Chemie,
Год журнала:
2021,
Номер
134(1)
Опубликована: Ноя. 2, 2021
Abstract
Condensed
phosphates
are
a
critically
important
class
of
molecules
in
biochemistry.
Non‐natural
analogues
for
various
applications,
such
as
single‐molecule
real‐time
DNA
sequencing.
Often,
contain
more
than
three
phosphate
units
their
oligophosphate
chain.
Consequently,
investigations
into
reactivity
enabling
new
ways
functionalization
and
oligophosphorylation
essential.
Here,
we
scrutinize
the
potential
to
act
arynophiles,
paving
way
follow‐up
reactions.
The
aryne
reaction
is
powerful
tool
to—depending
on
perspective—(oligo)phosphorylate
arenes
or
arylate
(oligo‐cyclo)phosphates.
Based
Kobayashi‐type
o‐silylaryltriflates,
enables
rapid
entry
broad
spectrum
arylated
products,
like
monophosphates,
diphosphates,
phosphodiesters
polyphosphates.
synthetic
these
transformations
demonstrated
by
efficient
syntheses
nucleotide
an
unprecedented
one‐flask
octaphosphorylation.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(49)
Опубликована: Окт. 18, 2023
Abstract
Anilines
are
potentially
high‐value
arylating
agents,
but
limited
by
the
low
reactivity
of
strong
C−N
bond.
We
show
that
reactive
intermediate
benzyne
can
be
used
to
both
activate
anilines,
and
set‐up
an
aryl
transfer
reaction
in
a
single
step.
The
does
not
require
any
transition
metal
catalysts
or
stoichiometric
organometallics,
establishes
metal‐free
route
valuable
biaryl
products
functionalizing
aniline
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
61(1)
Опубликована: Ноя. 2, 2021
Condensed
phosphates
are
a
critically
important
class
of
molecules
in
biochemistry.
Non-natural
analogues
for
various
applications,
such
as
single-molecule
real-time
DNA
sequencing.
Often,
contain
more
than
three
phosphate
units
their
oligophosphate
chain.
Consequently,
investigations
into
reactivity
enabling
new
ways
functionalization
and
oligophosphorylation
essential.
Here,
we
scrutinize
the
potential
to
act
arynophiles,
paving
way
follow-up
reactions.
The
aryne
reaction
is
powerful
tool
to-depending
on
perspective-(oligo)phosphorylate
arenes
or
arylate
(oligo-cyclo)phosphates.
Based
Kobayashi-type
o-silylaryltriflates,
enables
rapid
entry
broad
spectrum
arylated
products,
like
monophosphates,
diphosphates,
phosphodiesters
polyphosphates.
synthetic
these
transformations
demonstrated
by
efficient
syntheses
nucleotide
an
unprecedented
one-flask
octaphosphorylation.
Organic Process Research & Development,
Год журнала:
2023,
Номер
27(6), С. 1079 - 1093
Опубликована: Май 19, 2023
Tenofovir
alafenamide
fumarate
(TAF)
is
rising
as
a
mainstay
antiretroviral
agent
for
the
treatment
of
HIV
and
chronic
HBV
infections.
A
de
novo
practical
synthesis
TAF
circumventing
tenofovir
(PMPA)
has
been
accomplished
on
7
g
scale.
This
reimagined
TAF,
inspired
by
hitherto
uncharted
retrosynthetic
disconnection,
centers
P-alkylation
silylated
diphenyl
phosphonate
11
(as
acceptor)
with
methylthiomethyl
(MTM)
ether
derivative
12
donor)
in
presence
NIS/TfOH
combination
promoter
to
construct
strategic
carbon–phosphorus
bond.
PMPA-free
not
only
removes
intrinsic
drawbacks
encountered
PMPA-dependent
commercial
process
but
also
beneficial
diversification
synthetic
portfolio
TAF.
Furthermore,
this
type
reaction
defined
stereochemistry
could
be
deployed
late-stage
modification
druglike
molecules
natural
products
access
valuable
derivatives.
Royal Society of Chemistry eBooks,
Год журнала:
2024,
Номер
unknown, С. 109 - 231
Опубликована: Фев. 21, 2024
This
chapter
shows,
as
in
previous
years,
the
most
important
achievements
of
2021
year
area
organo-phosphorus
compounds
containing:
three
P–O
bonds
(Section
2:
phosphoric
acids
and
their
derivatives),
two
one
P–C
3:
phosphonic
derivatives)
well
4:
phosphinic
addition
to
phosphoryl
group
P═O,
present
all
groups
compounds.
Each
main
sections
covers
“synthesis
reactions”
including
pure
synthesis
without
applications,
biological
applications”
miscellaneous
directed
towards
non-biological
applications.
At
end
each
subsection,
corresponding
are
shown
for
hetero-analogues
which
phosphorus–oxygen
have
been
replaced
by
phosphorus–heteroatom
P–X
and/or
P═Y
(X,
Y
=
N,
S
or
Se).
The
subsection
on
quinquevalent
phosphorus
derivatives
catalysts
has
placed,
usual,
at
entire
chapter,
after
a
review
As
devoted
dominated
over
smaller
section
derivatives,
literature
references
these
remained
ratio
4
:
12
1.
A
dynamic,
five-fold
increase
number
works,
subject
chiral
catalysts,
recorded
this
year.
Organic Letters,
Год журнала:
2023,
Номер
25(38), С. 7030 - 7034
Опубликована: Сен. 15, 2023
An
efficient
method
for
generating
3-triazenylarynes
from
ortho-iodoaryl
triflate-type
precursors
was
developed.
The
generated
arynes
reacted
with
various
arynophiles
high
regioselectivity
because
of
the
triazenyl
group.
3-triazenylaryne
functioned
as
useful
intermediates
diverse
multisubstituted
aromatic
compounds
through
transformation
remaining
group
aryne
adducts
and
group-directed
ortho-C-H
functionalization.
Angewandte Chemie,
Год журнала:
2023,
Номер
135(49)
Опубликована: Окт. 18, 2023
Abstract
Anilines
are
potentially
high‐value
arylating
agents,
but
limited
by
the
low
reactivity
of
strong
C−N
bond.
We
show
that
reactive
intermediate
benzyne
can
be
used
to
both
activate
anilines,
and
set‐up
an
aryl
transfer
reaction
in
a
single
step.
The
does
not
require
any
transition
metal
catalysts
or
stoichiometric
organometallics,
establishes
metal‐free
route
valuable
biaryl
products
functionalizing
aniline
Chemical Communications,
Год журнала:
2023,
Номер
59(96), С. 14249 - 14252
Опубликована: Янв. 1, 2023
A
novel
aryne
species
3-triazenylaryne
has
been
developed
as
a
divergent
platform
for
the
generation
of
3-alkynylaryne
through
o
-triazenylarylboronic
acids.
Chemistry Letters,
Год журнала:
2021,
Номер
51(2), С. 94 - 98
Опубликована: Ноя. 19, 2021
Abstract
The
generation
of
3-azidoarynes
from
o-iodoaryl
triflate-type
precursors
was
achieved
using
a
silylmethyl
Grignard
reagent
as
the
activator.
azido
group
served
to
control
regioselectivity
reaction
with
arynophiles.
remaining
in
adduct
also
transformable
functional
group,
enabling
further
derivatization
various
nitrogen-containing
compounds.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(11), С. 8035 - 8040
Опубликована: Май 28, 2024
Mild,
metal-free,
and
operationally
simple
three-component
coupling
reactions
involving
arynes,
phosphites,
acrylates
have
been
achieved.
The
reaction
proceeded
well
with
α-
or
β-substituted
acrylates.
Additionally,
various
functional
groups
were
tolerated
under
these
conditions,
resulting
in
diverse
New Journal of Chemistry,
Год журнала:
2022,
Номер
46(35), С. 17049 - 17054
Опубликована: Янв. 1, 2022
Pre-functionalized
benzyne
precursors
5
,
6
and
10
bearing
a
phosphoryl
group
were
efficiently
synthesized
via
phospho-Fries
rearrangement
reaction
on
gram
scales,
directly
proceed
various
transformations
to
poly-substituted
organophosphorus
arenes
in
high
regioselectivity.
