Regio- and enantioselective synthesis of acyclic quaternary carbons via organocatalytic addition of organoborates to (Z)-Enediketones
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Янв. 13, 2024
Abstract
The
chemical
synthesis
of
molecules
with
closely
packed
atoms
having
their
bond
coordination
saturated
is
a
challenge
to
synthetic
chemists,
especially
when
three-dimensional
control
required.
organocatalyzed
asymmetric
acyclic
alkenylated,
alkynylated
and
heteroarylated
quaternary
carbon
stereocenters
via
1,4-conjugate
addition
here
catalyzed
by
3,3´-bisperfluorotoluyl-BINOL.
highly
useful
products
(31
examples)
are
produced
in
up
99%
yield
97:3
er
using
enediketone
substrates
potassium
trifluoroorganoborate
nucleophiles.
In
addition,
mechanistic
experiments
show
that
the
(
Z
)–isomer
reactive
form,
ketone
rotation
at
site
formation
needed
for
enantioselectivity,
favored
over
tertiary.
Density
functional
theory-based
calculations
reactivity
selectivity
depend
on
key
n→π*
donation
unbound
ketone’s
oxygen
lone
pair
boronate-coordinated
5-exo-trig
cyclic
ouroboros
transition
state.
Transformations
conjugate
carbon-bearing
building
blocks
proceed
good
yield.
Язык: Английский
Theoretical study of an N-heterocyclic carbene-catalyzed annulation reaction between an enal and a β-silyl enone: Mechanism and origin of stereoselectivity
Molecular Catalysis,
Год журнала:
2023,
Номер
551, С. 113621 - 113621
Опубликована: Окт. 27, 2023
Язык: Английский
Chiral Binaphthol-Catalyzed Enantioselective Conjugate Addition of Alkenyl and Arylboronic Acids to α,β-Unsaturated Cyclic N-Sulfonyl Ketimines
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(18), С. 13137 - 13149
Опубликована: Сен. 3, 2024
The
chiral
binaphthol-catalyzed
enantioselective
conjugate
addition
of
alkenylboronic
acids
and
heteroarylboronic
to
cyclic
Язык: Английский