Organic Letters,
Journal Year:
2021,
Volume and Issue:
23(2), P. 442 - 448
Published: Jan. 6, 2021
Highly
enantio-
and
regioselective
(3
+
2)
formal
cycloaddition
of
β-substituted
ene-
thioenecarbamates
as
well
cyclic
enamides
with
quinone
diimides
catalyzed
by
a
BINOL-
SPINOL-derived
phosphoric
acid
is
reported.
A
wide
variety
2,3-disubstituted
2-aminoindolines,
including
polycyclic
ones,
were
prepared
in
generally
high
yields
(up
to
98%)
moderate
complete
diastereoselectivities
most
cases
excellent
enantioselectivities
99%
ee).
Journal of the American Chemical Society,
Journal Year:
2018,
Volume and Issue:
140(45), P. 15181 - 15185
Published: Oct. 30, 2018
Enantio-
and
diastereoselective
conjunctive
cross-coupling
of
β-substituted
alkenylboron
"ate"
complexes
is
studied.
Whereas
β-substitution
shifts
the
chemoselectivity
catalytic
reaction
in
favor
Suzuki–Miyaura
product,
use
a
boronic
ester
ligand
derived
from
acenaphthoquinone
allows
process
to
even
with
substituted
substrates.
Journal of the American Chemical Society,
Journal Year:
2020,
Volume and Issue:
142(28), P. 11972 - 11977
Published: June 23, 2020
Photocatalytic
α-functionalization
of
amines
provides
a
mild
and
atom-economical
means
to
synthesize
α-branched
amines.
Prior
examples
featured
symmetrical
or
electronically
biased
substrates.
Here
we
report
controllable
in
which
regioselectivity
can
be
tuned
with
minor
changes
the
reaction
conditions.
Chemical Communications,
Journal Year:
2020,
Volume and Issue:
57(4), P. 441 - 459
Published: Dec. 10, 2020
Transition
metal-catalyzed
asymmetric
multicomponent
reactions
using
organoboron
compounds
have
been
utilized
extensively
for
C–B,
C–C,
and
other
bond-forming
reactions.
This
feature
article
highlights
the
important
discoveries
in
this
topic.
Journal of the American Chemical Society,
Journal Year:
2019,
Volume and Issue:
141(36), P. 14126 - 14130
Published: Aug. 27, 2019
α-Functionalization
of
alkyl
boronic
esters
and
homologation
aryl
by
regioselective
radical
C(sp3)-H
activation
in
boron-ate
complexes
is
reported.
Reaction
commercial
or
readily
accessed
acid
pinacol
with
lithium
reagents
provides
complexes.
Selective
α-C-H
abstraction
situ
generated
trifluoromethyl
radicals
leads
to
anions
that
undergo
electron
transfer
oxidation
followed
1,2-aryl/alkyl
migration
from
boron
carbon
give
the
α-arylated/alkylated
esters.
The
valuable
ester
functionality
remains
products
cheap
iodide
acts
as
oxidant
these
C-C
couplings.
1,2-alkyl
highly
stereospecific
allowing
access
stereoisomerically
pure
Journal of the American Chemical Society,
Journal Year:
2021,
Volume and Issue:
143(40), P. 16502 - 16511
Published: Sept. 28, 2021
Indole
dearomatization
is
an
important
strategy
to
access
indolines:
a
motif
present
in
variety
of
natural
products
and
biologically
active
molecules.
Herein,
method
for
transition-metal
catalyzed
regioselective
dearomative
arylboration
indoles
generate
diverse
indolines
presented.
The
accomplishes
intermolecular
simple
through
migratory
insertion
pathway
on
substrates
that
lack
activating
or
directing
groups
the
C2-
C3-positions.
Synthetically
useful
C3-borylated
can
be
accessed
change
N-protecting
group
high
regio-
diastereoselectivities
(up
>40:1
rr
dr)
from
readily
available
starting
materials.
Additionally,
origin
regioselectivity
was
explored
experimentally
computationally
uncover
remarkable
interplay
between
carbonyl
orientation
indole,
electronics
C2–C3
π-bond,
sterics.
enabled
first
enantioselective
synthesis
(−)-azamedicarpin.
Journal of the American Chemical Society,
Journal Year:
2020,
Volume and Issue:
142(12), P. 5515 - 5520
Published: March 7, 2020
The
broad
synthetic
utility
of
organoboron
compounds
stems
from
their
ready
ability
to
undergo
1,2-migrations.
Normally,
such
shifts
are
induced
by
α-leaving
groups
or
reactions
alkenyl
boronates
with
electrophiles.
Herein,
we
present
a
new
strategy
induce
1,2-metalate
rearrangements,
via
ring
expansion
vinylcyclopropyl
boronate
complexes
activated
This
leads
cyclopropane-stabilized
carbocation,
which
triggers
and
concomitant
rearrangement.
novel
process
delivers
medicinally
relevant
1,2-substituted
cyclobutyl
boronic
esters
high
levels
diastereoselectivity.
A
wide
range
organolithiums
Grignard
reagents,
electrophiles,
can
be
used.
methodology
was
applied
short,
stereoselective
synthesis
(±)-grandisol.
Computational
studies
indicate
that
the
reaction
proceeds
nonclassical
carbocation
followed
anti-1,2-migration.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
63(5)
Published: Dec. 15, 2023
The
construction
of
acyclic,
non-adjacent
1,3-stereogenic
centers,
prevalent
motifs
in
drugs
and
bioactive
molecules,
has
been
a
long-standing
synthetic
challenge
due
to
acyclic
nucleophiles
being
distant
from
the
chiral
environment.
In
this
study,
we
successfully
synthesized
highly
valuable
1,2-bis(boronic)
esters
featuring
nonadjacent
1,3-stereocenters.
Notably,
reaction
selectively
produces
migratory
coupling
products
rather
than
alternative
deborylative
allylation
or
direct
byproducts.
This
approach
introduces
new
activation
mode
for
selective
transformations
gem-diborylmethane
asymmetric
catalysis.
Additionally,
found
that
other
gem-diborylalkanes,
previously
challenging
steric
hindrance,
also
participated
reaction.
incorporation
1,2-bis(boryl)alkenes
facilitated
diversification
alkenyl
two
boron
moieties
our
target
compounds,
thereby
enabling
access
broad
array
versatile
molecules.
DFT
calculations
were
performed
elucidate
mechanism
shed
light
on
factors
responsible
observed
excellent
enantioselectivity
diastereoselectivity.
These
determined
arise
ligand-substrate
repulsions
syn-addition
transition
state.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(43)
Published: Sept. 6, 2023
Abstract
Methods
that
can
simultaneously
install
multiple
different
functional
groups
to
heteroarenes
via
C−H
functionalizations
are
valuable
for
complex
molecule
synthesis,
which,
however,
remain
challenging
realize.
Here
we
report
the
development
of
vicinal
di‐carbo‐functionalization
indoles
in
a
site‐
and
regioselective
manner,
enabled
by
palladium/norbornene
(Pd/NBE)
cooperative
catalysis.
The
reaction
is
initiated
Pd(II)‐mediated
C3‐metalation
specifically
promoted
C1‐substituted
NBEs.
mild,
scalable,
robust
conditions
allow
good
substrate
scope
excellent
group
tolerance.
resulting
C2‐arylated
C3‐alkenylated
be
converted
diverse
synthetically
useful
scaffolds.
combined
experimental
computational
mechanistic
study
reveals
unique
role
NBE
accelerating
turnover‐limiting
oxidative
addition
step.
