Organic Letters,
Journal Year:
2023,
Volume and Issue:
unknown
Published: Dec. 29, 2023
An
one-pot
organo-
and
iodine
sequential
catalysis
strategy
for
reactions
of
amides
with
pyrazole-based
primary
amines
was
described
to
synthesize
chiral
α-amino
a
quaternary
stereocenter.
This
methodology
exhibited
strong
asymmetric
induction,
resulting
in
typical
enantiomeric
excess
value
exceeding
99%
diastereoselectivity
up
>99:1
dr.
Moreover,
the
reaction
conducted
without
use
any
metals
or
bases.
Organic & Biomolecular Chemistry,
Journal Year:
2023,
Volume and Issue:
21(35), P. 7036 - 7051
Published: Jan. 1, 2023
This
review
provides
a
comprehensive
summary
of
the
utilization
ammonia
replacements
in
synthesizing
protected
and
free
primary
amines,
encompassing
both
traditional
reagents
latest
developments.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(7), P. 4357 - 4362
Published: Feb. 9, 2024
The
widespread
occurrence
and
synthetic
accessibility
of
amides
render
them
valuable
precursors
for
the
synthesis
diverse
nitrogen-containing
compounds.
Herein,
we
present
a
metal-free
streamlined
strategy
quaternary
α-aminophosphonates.
This
approach
involves
sequential
deoxygenative
nucleophilic
phosphonation
versatile
electrophilic
alkylation
secondary
in
one-pot
fashion.
Notably,
this
method
enables
direct
bis-functionalization
with
both
nucleophiles
electrophiles
first
time,
simple
derivatization
leading
to
free
α-aminophosphonates
by
hydrolysis.
protocol
has
advantages
operational
simplicity,
broad
functional-group
compatibility,
environmental
friendliness,
scalability
multigram
quantities.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(8), P. 1601 - 1606
Published: Feb. 19, 2024
An
enantioselective
difunctionalization
of
activated
alkynes
using
chiral
sulfinamide
reagents
is
developed.
It
an
atom
and
chirality
transfer
process
that
allows
for
the
modular
synthesis
optically
active
α-amino
acid
derivatives
under
mild
conditions.
The
reaction
proceeds
through
acid-catalyzed
[2,3]-sigmatropic
rearrangement
mechanism
with
predictable
stereochemistry
a
broad
scope.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(35), P. 24699 - 24707
Published: Aug. 24, 2024
Modulating
the
basicity
of
alkylamines
is
a
crucial
factor
in
drug
design.
Consequently,
with
proximal
amide,
ester,
or
ketone
have
become
privileged
features
many
pharmaceutical
candidates.
The
impact
α-amino
carbonyls
has
made
development
new
methods
for
their
preparation
continuous
challenge
synthesis.
Here,
we
describe
practical
strategy
that
provides
modular
and
programmable
synthesis
wide
range
carbonyls.
generality
this
process
possible
by
an
extremely
mild
method
to
generate
carbamoyl
radicals,
proceeding
via
Lewis
acid-visible-light-mediated
Norrish
type-I
fragmentation
tailored
carboxamide
reagent
intercepted
through
addition
situ
generated
unbiased
imines.
Aside
from
reaction's
broad
scope
each
component,
its
capacity
draw
on
plentiful
diversely
populated
amine
carbonyl
feedstocks
showcased
two-dimensional
array
used
construct
library
novel,
assay-ready,
amides.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(40), P. 27267 - 27273
Published: Sept. 27, 2024
α-Amino
esters
are
precursors
to
noncanonical
amino
acids
used
in
developing
small-molecule
therapeutics,
biologics,
and
tools
chemical
biology.
α-C-H
amination
of
abundant
inexpensive
carboxylic
acid
through
nitrene
transfer
presents
a
direct
approach
α-amino
esters.
Methods
for
nitrene-mediated
the
protic
bonds
esters,
however,
underdeveloped.
This
gap
arises
because
hydrogen
atom
abstraction
(HAA)
C-H
by
electrophilic
metal-nitrenoids
is
slow:
preferentially
react
with
polarity-matched,
hydridic
bonds,
even
when
weaker
present.
study
describes
discovery
evolution
highly
stable
protoglobin
transferases
that
catalyze
enantioselective
intermolecular
We
developed
high-throughput
assay
evaluate
activity
enantioselectivity
mutant
enzymes
together
their
sequences
using
Every
Variant
Sequencing
(evSeq)
method.
The
enabled
identification
enantiodivergent
function
at
ambient
conditions
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 9, 2025
Treatment
of
multisubstituted
NH-enesulfinamides
with
tosyl
isocyanate
(TsNCO)
at
room
temperature
results
in
the
formation
α-tosylcarbamoyloxy
N-sulfenyl
ketimines
high
enantioselectivity.
This
process
is
believed
to
proceed
via
a
vinylogous
aza-Pummerer-type
reaction
pathway
which
sulfinyl
oxygen
atom
enesulfinamides
undergoes
nucleophilic
attack
on
isocyanate,
triggering
subsequent
transformations
that
enable
transfer
chirality
from
sulfur
carbon.
Science Advances,
Journal Year:
2025,
Volume and Issue:
11(14)
Published: April 4, 2025
Amines
are
ubiquitous
components
in
pharmaceuticals.
Increasing
saturated
substitutions
(
sp
3
-hybridized
carbon)
at
the
amino
center
and
number
of
chiral
centers
can
enrich
molecular
diversity
chemical
space,
ultimately
enhancing
success
drug
development.
However,
synthesis
such
advanced
amines
is
challenging
due
to
a
higher
level
structural
complexity
stereo-control.
Here,
we
report
modular
protocol
for
short
de
novo
bis-α-chiral
amines.
This
uses
commercially
available
Ellman
sulfinamide,
tert
-butanesulfinamide
t
BS),
as
exclusive
source
selectively
produce
all
possible
stereoisomers.
Sequential
formation
contiguous
α-amino
carbons
achieved
by
chirality
induction
transfer
mechanisms
that
both
enabled
BS,
stereoselective
imine
functionalization
alkyne-participated
rearrangement
reaction.
The
second
step
developed
crucial
high
diastereoselectivity,
which
problematic
previous
methods.
other
coupling
partners
used
this
abundant
feedstocks,
providing
desirable
products.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(22), P. 4156 - 4161
Published: May 25, 2023
An
aza-variation
on
[2,3]-sigmatropic
rearrangement
of
allylic
sulfimides
was
developed.
In
this
process,
enolization
N-acyl
iminosulfinamides
followed
by
O-silylation
to
generate
O-silyl
N-iminosulfinyl
N,O-ketene
aminal
intermediates,
which
undergo
a
[2,3]-shift
afford
α-sulfenylamino
imidates
that
were
converted
the
corresponding
carboxamides
after
desilylation
triggered
acidic
aqueous
workup.
Chirality
is
transferred
from
sulfur
stereocenter
α-carbon,
thereby
enabling
enantioselective
installation
an
amino
group
at
α-position
amides.
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(9)
Published: Jan. 5, 2024
Abstract
Sulfenyl
imidinium
salts
are
a
virtually
unexplored
class
of
intermediates
in
organic
chemistry.
Herein,
we
demonstrate
how
sulfonium
rearrangements
can
be
deployed
to
access
these
versatile
synthetic
intermediates,
bearing
three
contiguous
(and
congested)
stereogenic
centers,
with
high
levels
selectivity.
The
value
the
scaffold
was
unraveled
by
selective
transformations
into
range
building
blocks,
including
1,4‐dicarbonyl
derivatives
and
sulfonolactones.
