Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(12), P. 7905 - 7914
Published: March 13, 2024
Experimental
and
computational
studies
illuminating
the
factors
that
guide
metal-centered
stereogenicity
and,
therefrom,
selectivity
in
transfer
hydrogenative
carbonyl
additions
of
alcohol
proelectrophiles
catalyzed
by
chiral-at-metal-and-ligand
octahedral
d6
metal
ions,
iridium(III)
ruthenium(II),
are
described.
To
augment
or
invert
regio-,
diastereo-,
enantioselectivity,
predominantly
one
from
among
as
many
15
diastereomeric-at-metal
complexes
is
required.
For
catalysts,
cyclometalation
assists
defining
stereocenter,
for
ruthenium(II)
iodide
counterions
play
a
key
role.
Whereas
classical
strategies
to
promote
catalysis
aim
high-symmetry
transition
states,
well-defined
low-symmetry
states
can
unlock
selectivities
otherwise
difficult
achieve
inaccessible.
Chemical Reviews,
Journal Year:
2024,
Volume and Issue:
124(9), P. 6078 - 6144
Published: April 17, 2024
Alcohols
are
abundant
and
attractive
feedstock
molecules
for
organic
synthesis.
Many
methods
their
functionalization
require
them
to
first
be
converted
into
a
more
activated
derivative,
while
recent
years
have
seen
vast
increase
in
the
number
of
complexity-building
transformations
that
directly
harness
unprotected
alcohols.
This
Review
discusses
how
transition
metal
catalysis
can
used
toward
this
goal.
These
broadly
classified
three
categories.
Deoxygenative
functionalizations,
representing
derivatization
C–O
bond,
enable
alcohol
act
as
leaving
group
formation
new
C–C
bonds.
Etherifications,
characterized
by
O–H
represent
classical
reactivity
has
been
modernized
include
mild
reaction
conditions,
diverse
partners,
high
selectivities.
Lastly,
chain
reactions
described,
wherein
acts
mediator
formal
C–H
alkyl
backbone.
Each
these
classes
transformation
will
discussed
context
intermolecular
arylation,
alkylation,
related
reactions,
illustrating
alcohols
harnessed
Chemistry - A European Journal,
Journal Year:
2021,
Volume and Issue:
27(52), P. 13107 - 13116
Published: June 29, 2021
Abstract
The
use
of
allenes
and
1,3‐dienes
as
chiral
allylmetal
pronucleophiles
in
intermolecular
catalytic
enantioselective
reductive
additions
to
aldehydes,
ketones,
imines,
carbon
dioxide
other
C=X
electrophiles
is
exhaustively
catalogued
together
with
redox‐neutral
hydrogen
auto‐transfer
processes.
Coverage
limited
processes
that
result
both
C−H
C−C
bond
formation.
alkynes
latent
multicomponent
allylations
involving
dienes
not
covered.
As
illustrated
this
review,
the
ability
serve
tractable
non‐metallic
has
evoked
many
useful
transformations
have
no
counterpart
traditional
chemistry.
The Journal of Organic Chemistry,
Journal Year:
2021,
Volume and Issue:
87(4), P. 1880 - 1897
Published: Nov. 15, 2021
Parallel
library
synthesis
is
an
important
tool
for
drug
discovery
because
it
enables
the
of
closely
related
analogues
in
parallel
via
robust
and
general
synthetic
transformations.
In
this
perspective,
we
analyzed
methodologies
used
>5000
libraries
representing
15
prevalent
The
data
set
contains
complex
substrates
diverse
arrays
building
blocks
over
last
14
years
at
AbbVie.
that
have
demonstrated
robustness
generality
with
proven
success
are
described
along
their
substrate
scopes.
evolution
past
decade
discussed.
We
also
highlight
combination
high-throughput
experimentation
will
continue
to
facilitate
library-amenable
discovery.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(13), P. 5985 - 5995
Published: March 26, 2022
The
selective
reductive
coupling
of
vinyl
heteroarenes
with
aldehydes
and
ketones
represents
a
versatile
approach
for
the
rapid
construction
enantiomerically
enriched
secondary
tertiary
alcohols,
respectively.
Herein,
we
demonstrate
CuH-catalyzed
regiodivergent
carbonyl-containing
electrophiles,
in
which
selectivity
is
controlled
by
ancillary
ligand.
This
leverages
an
situ
generated
benzyl-
or
dearomatized
allyl-Cu
intermediate,
yielding
either
exocyclic
addition
products,
method
exhibits
excellent
regio-,
diastereo-,
enantioselectivity
tolerates
range
common
functional
groups
heterocycles.
dearomative
pathway
allows
direct
access
to
variety
functionalized
saturated
heterocyclic
structures.
reaction
mechanism
was
probed
using
combination
experimental
computational
approach.
Density
theory
studies
suggest
that
ligand-controlled
regioselectivity
results
from
C-H/π
interaction
steric
repulsion
transition
states,
leading
major
minor
regioisomers,
Hydrocupration
heteroarene
pronucleophile
enantiodetermining
step,
whereas
diastereoselectivity
enforced
interactions
between
benzylic
intermediate
substrates
six-membered
cyclic
state.
ACS Catalysis,
Journal Year:
2022,
Volume and Issue:
12(14), P. 8164 - 8174
Published: June 23, 2022
The
use
of
alkynes
as
vinylmetal
pronucleophiles
in
intermolecular
enantioselective
metal-catalyzed
carbonyl
and
imine
reductive
couplings
to
form
allylic
alcohols
amines
is
surveyed.
Related
hydrogen
auto-transfer
processes,
wherein
or
serve
dually
reductants
proelectrophiles,
also
are
cataloged,
applications
target-oriented
synthesis.
These
processes
represent
an
emerging
alternative
the
stoichiometric
reagents
Nozaki-Hiyama-Kishi
(NHK)
reactions
alkenylation.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(35)
Published: June 30, 2023
An
atroposelective
Ir-catalyzed
dynamic
kinetic
resolution
(DKR)
of
2-(quinolin-8-yl)benzaldehydes/1-naphthaldehydes
by
transfer
hydrogenative
coupling
allyl
acetate
is
disclosed.
The
allylation
reaction
takes
place
with
simultaneous
installation
central
and
axial
chirality,
reaching
high
diastereoselectivities
excellent
enantiomeric
excesses
when
ortho-cyclometalated
iridium-DM-BINAP
used
as
the
catalyst.
racemization
substrates
occurs
through
a
designed
transient
Lewis
acid-base
interaction
between
quinoline
nitrogen
atom
aldehyde
carbonyl
group.
ChemCatChem,
Journal Year:
2024,
Volume and Issue:
16(14)
Published: March 7, 2024
Abstract
Direct
asymmetric
hydrogenation
(AH)
and
transfer
(ATH)
are
among
the
most
efficient
approaches
to
produce
chiral
building
blocks.
Recently,
these
types
of
transformations
have
witnessed
a
shift
towards
use
molecular
catalysts
based
on
earth‐abundant
transition
metals
due
their
ready
availability,
economic
advantage,
novel
properties.
With
particular
regard
manganese,
catalyst
development
has
seen
both
efficiency
substrate
scope
in
AH
ATH
greatly
improved,
with
emergence
large
number
well‐defined
Mn‐complexes
employed
this
field.
The
reaction
includes
C=O
bonds,
reduction
C=N
bonds
reductive
C=C
bonds.
Herein,
our
survey
area
focuses
catalytic
activity
such
complexes,
versatility
routes
convert
substrates
target
molecules.
We
consider
collected
findings
article
will
be
helpful
reader
by
providing
an
insight
into
ligand
design,
thereby
aiding
future
development.
Moreover,
review
is
aimed
at
highlighting
remarkable
progress
made
last
seven
years
manganese
complexes
for
enantioselective
reduction.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 6, 2025
A
novel
mechanism
for
N-heteroaryl
C–H
functionalization
via
dearomative
addition-hydrogen
autotransfer
is
described.
Upon
exposure
to
the
catalyst
derived
from
RuHCl(CO)(PPh3)3
and
Xantphos,
dienes
1a–1g
suffer
hydroruthenation
form
allylruthenium
nucleophiles
that
engage
in
addition-β-hydride
elimination
furnish
branched
products
of
C–C
coupling
3a–3s
4a–4f.
Oxidative
cleavage
isoprene
adducts
3j,
3k,
3l,
3n
followed
by
ruthenium-catalyzed
dynamic
kinetic
asymmetric
ketone
reduction
provides
enantiomerically
enriched
N-heteroarylethyl
alcohols
6a–6d
and,
therefrom,
amines
7a–7d.
Density
functional
theory
calculations
correlate
experimentally
observed
regioselectivities
with
magnitude
LUMO
coefficients
corroborate
rate-determining
addition.
In
presence
2-propanol
trifluoroethanol,
dearomatized
pyrimidine
2a
quinazoline
2n
were
isolated
characterized.