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Cl
H
N N N perbenzoate TFA
O based
on
pyridine
has
been
Cl
CuBr
Benzene designed.
The
norbornane
MgSO4, Cyclohexane 2) NaOH
H2O, MeOH N core
is
accessible
from
Boc norbornadiene
through
7
1) H2, Pd/C, EtOH
LiAlH4
THF oxonorborane.
Addi.on
of
2) NaBH4, EtOH
O O nucelophiles
to
this
ketone
OH
O O OH have
proved
some
what
H2, Pd/C
PCC, Silica gel, troublesome.
Nonetheless
EtOH DCM
products
for
preliminary
LiAlH4, THF
N N
Me2SO4
KH N studies
have
been
synthesised.
DMF
Boc Boc
2-Li-Pyr
THF
2-Li-DMAP, THF
Unfortunately
the
pyridyl
N analogue
appears
to
be
unable
To
promote
the
desired
chemistry
over
compe.ng
side
reac.ons
a
to
transfer
its
electron
to
PTP.
distant
H
atom
must
be
held
close
to
the
nitrogen
centre.
It
is
also
It
is
believed
the
DMAP
advantageous
to
deac.vate
α-‐H
atoms.
This
amine
has
been
designed
N
OH
N
OH
analogue
will
be
more
with
these
constraints
in
mind.
The
key
step
in
the
synthe.c
scheme
successful
once
its
synthesis
is
is
a
[4,3]
cycloaddi.on
reac.on
which
builds
the
tricyclic
core.
achieved.
6
5
Re(bipy)(CO)3Cl
Photocatalysts
Conclusions
To
show
wide
applicability
of
our
amine
•
Designed
and
synthesised
a
renewable
amine
for
CO2
reduc.on
Cl
in
CO2
reduc.ons
we
must
inves.gate
•
No
requirement
for
sacrificial
electron
donors
in
CO2
reduc.on
N CO the
use
of
organometallic
photo-‐ •
Coupled
photochemical
CO2
reduc.on
and
water
spliSng
reac.ons
Re catalysts.
We
start
our
inves.ga.on
•
Developed
prototype
ar.ficial
photosynthesis
of
formic
acid
N CO
CO with
Re(bipy)(CO)3Cl.
Preliminary
•
Preliminary
results
indicate
wider
applicability
of
our
amine
results
include
a
reduc.on
in
•
Second
genera.on
amines
in
development
phosphorescence
life.me
with
Acknowledgements
increasing
amine
concentra.on,
We
wish
to
thank
everybody
involved
in
the
project;
especially
the
detec.on
of
reduc.on
product
(CO)
by
George
group
in
NoSngham
and
the
POC
centre
Cardiff.
We
also
wish
GC-‐TCD;
and
produc.on
of
alkene
to
thank
those
who
have
funded
our
work:
Leverhumle
Trust,
EPSRC
detected
by
NMR
studies.
All
these
and
HEFCW.
results
indicate
that
our
amine
is
capable
of
reducing
CO2
with
a
Re(bipy)
References
(CO)3Cl
photocatalyst,
however
these
B.
K.
Carpenter
et
al,
JACS.
2008,
130,
3169-‐3180
results
are
all
preliminary
and
we
seek
B.
K.
Carpenter
et
al,
Nature
Chem.
2011,
3,
301-‐303
B.
K.
Carpenter,
J.
Phys.
Chem.
A
2007,
111,
3719-‐3726
to
further
quan.fy
these
results.
We
F.
Williams
et
al,
Chem.
Eur.
J.
2004,
10,
5524-‐5534
BoTom:
Photochemical
sample
Top:
Photochemical
sample
spiked
with
authen.c
alkene
must
also
extend
the
work
to
more
E.
Fujita
et
al,
Acc.
Chem.
Res.
2009,
42,
1983-‐1994
photocatalysts.