The green chemistry paradigm in modern organic synthesis
Russian Chemical Reviews,
Год журнала:
2023,
Номер
92(12), С. RCR5104 - RCR5104
Опубликована: Дек. 1, 2023
After
the
appearance
of
green
chemistry
concept,
which
was
introduced
in
vocabulary
early
1990s,
its
main
statements
have
been
continuously
developed
and
modified.
Currently,
there
are
10–12
cornerstones
that
should
form
basis
for
an
ideal
chemical
process.
This
review
analyzes
accumulated
experience
achievements
towards
design
products
processes
reduce
or
eliminate
use
generation
hazardous
substances.
The
presents
views
leading
Russian
scientists
specializing
various
fields
this
subject,
including
homogeneous
heterogeneous
catalysis,
fine
basic
organic
synthesis,
electrochemistry,
polymer
chemistry,
based
on
bio-renewable
feedstocks
energetic
compounds
materials.
A
new
approach
to
quantitative
evaluation
environmental
friendliness
by
authors
is
described.
<br>
bibliography
includes
1761.
Язык: Английский
Combined Computational and Experimental Study Reveals Complex Mechanistic Landscape of Brønsted Acid-Catalyzed Silane-Dependent P═O Reduction
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(20), С. 13983 - 13999
Опубликована: Май 13, 2024
The
reaction
mechanism
of
Brønsted
acid-catalyzed
silane-dependent
P═O
reduction
has
been
elucidated
through
combined
computational
and
experimental
methods.
Due
to
its
remarkable
chemo-
stereoselective
nature,
the
acid/silane
system
widely
employed
in
organophosphine-catalyzed
transformations
involving
P(V)/P(III)
redox
cycle.
However,
full
mechanistic
profile
this
type
yet
be
clearly
established
date.
Supported
by
both
DFT
studies,
our
research
reveals
that
likely
proceeds
mechanisms
other
than
accepted
"dual
activation
mode
silyl
ester"
or
"acid-mediated
direct
activation"
mechanism.
We
propose
although
may
vary
with
substitution
patterns
silane
species,
acid
generally
activates
rather
group
transition
structures.
proposed
differs
significantly
from
associated
traditional
C═O
reduction.
uniqueness
originates
dominant
Si/O═P
orbital
interactions
structures
P/H–Si
interactions.
comprehensive
landscape
provided
us
will
serve
as
a
guidance
for
rational
design
development
more
efficient
systems
well
novel
reactions
Язык: Английский
Photocatalytic Phosphine-Mediated Deoxygenative [3 + 2] Cycloaddition of α,β-Unsaturated Carbonyls and Alkenes
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 22, 2025
Tertiary
phosphine
is
a
powerful
nucleophile
that
enables
numerous
synthetically
important
reactions.
However,
the
exclusive
reliance
on
two-electron
pathway
has
restricted
development
of
chemistry.
We
report
here
visible
light
photocatalytic
phosphine-mediated
deoxygenative
[3
+
2]
cycloaddition
α,β-unsaturated
carbonyls
and
activated
alkenes,
providing
facile
access
to
polysubstituted
cyclopentenes
from
readily
accessible
starting
materials
in
promising
yields
with
good
substrate
scope.
Mechanistic
investigations
corroborate
transient
involvement
radical
cation
consequent
α-addition
(α
electron-withdrawing
groups)
C-C
double
bonds
due
inherent
electrophilicity
cation,
as
opposed
traditional
nucleophilic
β-addition
phosphine.
The
ensuing
single
electron
transfer
reduction,
Michael
addition,
1,4-proton
cascade
furnish
phosphorus
ylide,
which
undergoes
an
intramolecular
Wittig
reaction
finish
construction
cyclopentenes.
This
work
demonstrates
tertiary
can
serve
convenient
reagent
for
carbonyl
deoxygenation
act
traceless
directing
group
controllable
cross-coupling
two
distinct
new
avenues
expand
frontiers
chemistry
synthetic
Язык: Английский
Iridium-Catalyzed Enantioselective Formal α-Allylic Alkylation of Acrylonitrile
Organic Letters,
Год журнала:
2023,
Номер
25(24), С. 4520 - 4524
Опубликована: Июнь 13, 2023
A
highly
enantioselective
formal
α-allylic
alkylation
of
acrylonitrile
is
developed
using
4-cyano-3-oxotetrahydrothiophene
(c-THT)
as
a
safe
and
easy-to-handle
surrogate
acrylonitrile.
This
two-step
process
consists
an
Ir(I)/(P,olefin)-catalyzed
branched-selective
allylic
easily
accessible
branched
rac-allylic
alcohols
the
electrophile
followed
by
retro-Dieckmann/retro-Michael
fragmentation
shown
to
be
applicable
for
synthesis
acrylates
well
acrolein.
Язык: Английский
Carbon Nucleophile-Initiated Rauhut–Currier Reaction: An Atom-Economical Synthesis of Highly Functionalized Carbocycles
The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
88(16), С. 12069 - 12073
Опубликована: Июль 27, 2023
A
Rauhut-Currier
reaction
cascade
is
achieved
in
the
presence
of
carbon
nucleophiles
under
mild
conditions.
This
original
atom-economical
transformation
enables
an
efficient
one-pot
synthesis
densely
substituted
carbocycles
from
readily
accessible
substrates.
The
key
promoter
role
cesium
cation
process
was
demonstrated.
Язык: Английский
Phosphine-catalyzed Rauhut–Currier reaction of γ-alkyl allenoate and subsequent trapping using the Diels–Alder reaction
Chemical Communications,
Год журнала:
2023,
Номер
59(78), С. 11720 - 11723
Опубликована: Янв. 1, 2023
We
have
disclosed
a
Rauhut-Currier
reaction
of
γ-alkyl-substituted
allenoate,
catalyzed
by
L-valine-derived
amide
phosphine,
to
form
trisubstitued
which
was
trapped
maleimide
or
DMAD
via
the
Diels-Alder
reaction.
Exo-bicyclic
succinimide
derivatives
including
three
continuous
stereocenters
with
an
exo-carbon-carbon
double
bound
were
constructed
in
up
quantitative
yields
high
stereospecificity.
Язык: Английский
Iridium-Catalyzed Enantioselective Formal α-Allylic Alkylation of Acrylonitrile
Опубликована: Май 11, 2023
A
highly
enantioselective
formal
α-allylic
alkylation
of
acrylonitrile
is
developed
using
4-cyano-3-oxotetrahydrothiophene
(c-THT)
as
a
safe
and
easy-to-handle
surrogate
acrylonitrile.
This
two-step
process
consists
an
Ir/(P,olefin)-catalyzed
branched-selective
allylic
easily
accessible
branched
rac-allylic
alcohols
the
electrophile
followed
by
retro-Dieckmann/retro-Michael
fragmentation
shown
to
be
applicable
for
synthesis
acrylates
acrolein.
Язык: Английский
Phosphine-Promoted Intramolecular Rauhut-Currier/Wittig Reaction Cascade to Access (Hetero)arene-Fused Diquinanes
Organic & Biomolecular Chemistry,
Год журнала:
2024,
Номер
22(28), С. 5718 - 5723
Опубликована: Янв. 1, 2024
We
describe
the
first
phosphine-promoted
intramolecular
Rauhut-Currier
reaction
that
triggers
an
Wittig
process
assembling
new
classes
of
diquinanes.
The
one-pot
strategy
provides
ready
access
to
simple
diquinanes
and
various
(hetero)arene-fused
incorporated
with
up
two
contiguous
all-carbon
quaternary
centers
under
metal-free
neutral
conditions.
showcased
generality
method
on
a
broad
range
substrates
demonstrated
its
synthetic
utility
in
accessing
advanced
intermediates
relevant
natural
product
synthesis
material
science.
Язык: Английский
Phosphine-Catalyzed Crossed Rauhut–Currier-Type Coupling and [3 + 2]-Cycloaddition of 2-Alkylidene-3-oxindoles with Alkenes and Allenes to Access β,γ-Unsaturated Enones and Polycyclic Oxindoles
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(18), С. 13263 - 13271
Опубликована: Сен. 6, 2024
Dihydroazepino[1,2-
Язык: Английский