Synthesis,
Год журнала:
2023,
Номер
55(20), С. 3209 - 3238
Опубликована: Апрель 28, 2023
Abstract
Silyl
esters
have
been
exploited
as
metastable
reaction
intermediates,
both
purposefully
and
unintentionally,
since
at
least
the
1960s.
Their
reactivity
is
broadly
related
to
substituents
on
silicon,
in
this
way
their
properties
can
be
readily
modulated.
unique
profiles
that
used
generate
downstream
products
of
a
range
functionalities,
because
many
excellent
methods
for
synthesis
variety
value-added
chemicals
developed.
Furthermore,
frequent
use
hydrosilanes
terminal
reductants
catalytic
processes,
silyl
ester
intermediates
are
likely
more
commonly
utilized
by
synthetic
chemists
than
currently
realized.
This
review
comprehensively
summarizes
reactions
known
take
advantage
reactive
discusses
examples
proceed
an
unanticipated
manner
through
intermediates.
1
Introduction
2
Synthesis
Esters
3
Making
Amides
from
3.1
Amidation
Using
Chlorosilanes
3.2
Azasilanes
3.3
Oxysilanes
3.4
Hydrosilanes
3.5
Amine
Formation
via
Amidation/Reduction
3.6
Miscellaneous
4
Mechanistic
Investigations
4.1
Mechanism
4.2
4.3
Oxy-
or
5
6
Aldehydes,
Alcohols,
Amines,
Alkanes
Reduction
6.1
Aldehyde
Metal-Free
6.2
Metal-Mediated
6.3
Alcohol
6.4
6.5
Alkane
7
Acid
Chlorides
8
In
Situ
Generated
Ramifications
Catalysis
9
Conclusion
Communications Chemistry,
Год журнала:
2023,
Номер
6(1)
Опубликована: Окт. 26, 2023
Accessible
drug
modalities
have
continued
to
increase
in
number
recent
years.
Peptides
play
a
central
role
as
pharmaceuticals
and
biomaterials
these
new
modalities.
Although
traditional
peptide
synthesis
using
chain-elongation
from
C-
N-terminus
is
reliable,
it
produces
large
quantities
of
chemical
waste
derived
protecting
groups
condensation
reagents,
which
place
heavy
burden
on
the
environment.
Here
we
report
an
alternative
N-to-C
elongation
strategy
utilizing
catalytic
thioacid
formation
oxidative
bond
with
main
chain-unprotected
amino
acids
under
aerobic
conditions.
This
method
applicable
both
iterative
couplings
convergent
fragment
without
requiring
elaborate
reagents
group
manipulations.
A
recyclable
N-hydroxy
pyridone
additive
effectively
suppresses
epimerization
at
elongating
chain.
We
demonstrate
practicality
this
by
showcasing
straightforward
nonapeptide
DSIP.
further
opens
door
clean
atom-efficient
synthesis.
Chemistry - A European Journal,
Год журнала:
2024,
Номер
unknown
Опубликована: Авг. 23, 2024
Abstract
We
have
developed
radical
C‐glycosylation
using
photoexcitable
unprotected
glycosyl
borate.
The
direct
excitation
of
borate
under
visible
light
irradiation
enabled
the
generation
anomeric
without
any
photoredox
catalysts.
in
situ
generated
was
applicable
to
addition
such
as
Giese‐type
and
Minisci‐type
reaction
introduce
alkyl
heteroaryl
groups
at
position.
In
addition,
radical–radical
coupling
between
acyl
imidazolide
provided
C‐glycosides.
Journal of the American Chemical Society,
Год журнала:
2019,
Номер
141(48), С. 18926 - 18931
Опубликована: Ноя. 15, 2019
A
tantalum-catalyzed
solvent-free
approach
for
the
construction
of
amide
bonds
with
1-(trimethylsilyl)imidazole
is
developed,
and
mild
reaction
conditions
are
applicable
to
a
wide
variety
electrophilic
amino
acid
homologues.
This
delivers
new
class
peptides
in
high
yields
without
any
epimerization.
The Journal of Organic Chemistry,
Год журнала:
2022,
Номер
87(11), С. 7308 - 7318
Опубликована: Май 12, 2022
Thionyl
fluoride
(SOF2)
is
an
underutilized
reagent
that
yet
to
be
extensively
studied
for
its
synthetic
applications.
We
previously
reported
it
a
powerful
both
the
rapid
syntheses
of
acyl
fluorides
and
one-pot
peptide
couplings,
but
full
scope
these
nucleophilic
substitutions
had
not
been
explored.
Herein,
we
report
thionyl
fluoride-mediated
peptides
amides
(35
examples,
45–99%
yields)
were
explored
in
our
previous
study.
The
was
also
expanded
encompass
esters
(24
64–99%
thioesters
(11
24–96%
yields).
In
addition,
demonstrate
reactions
can
extended
beyond
mild
reductions
carboxylic
acids
using
NaBH4
(13
33–80%
Synthesis,
Год журнала:
2023,
Номер
55(20), С. 3209 - 3238
Опубликована: Апрель 28, 2023
Abstract
Silyl
esters
have
been
exploited
as
metastable
reaction
intermediates,
both
purposefully
and
unintentionally,
since
at
least
the
1960s.
Their
reactivity
is
broadly
related
to
substituents
on
silicon,
in
this
way
their
properties
can
be
readily
modulated.
unique
profiles
that
used
generate
downstream
products
of
a
range
functionalities,
because
many
excellent
methods
for
synthesis
variety
value-added
chemicals
developed.
Furthermore,
frequent
use
hydrosilanes
terminal
reductants
catalytic
processes,
silyl
ester
intermediates
are
likely
more
commonly
utilized
by
synthetic
chemists
than
currently
realized.
This
review
comprehensively
summarizes
reactions
known
take
advantage
reactive
discusses
examples
proceed
an
unanticipated
manner
through
intermediates.
1
Introduction
2
Synthesis
Esters
3
Making
Amides
from
3.1
Amidation
Using
Chlorosilanes
3.2
Azasilanes
3.3
Oxysilanes
3.4
Hydrosilanes
3.5
Amine
Formation
via
Amidation/Reduction
3.6
Miscellaneous
4
Mechanistic
Investigations
4.1
Mechanism
4.2
4.3
Oxy-
or
5
6
Aldehydes,
Alcohols,
Amines,
Alkanes
Reduction
6.1
Aldehyde
Metal-Free
6.2
Metal-Mediated
6.3
Alcohol
6.4
6.5
Alkane
7
Acid
Chlorides
8
In
Situ
Generated
Ramifications
Catalysis
9
Conclusion
