10.1021/jo9720041.s001
Thomas W. Bell
Thomas W.
Bell
Peter J. Cragg
Peter J.
Cragg
Albert Firestone
Albert
Firestone
Albert D.-I. Kwok
Albert D.-I.
Kwok
Jia Liu
Jia
Liu
Richard Ludwig
Richard
Ludwig
Andrej Sodoma
Andrej
Sodoma
Molecular Architecture. 2. Synthesis and Metal Complexation of
Heptacyclic Terpyridyl Molecular Clefts
American Chemical Society
1998
heptacyclic framework
Alkali metal complexes
2. Synthesis
functionalized derivatives
heptacyclic terpyridyls
alkali metal complexes
Pentadentate host 6
Metal Complexation
hexadentate crown ethers
preorganized host compounds
group dipoles
heptacyclic terpyridyls 6
pentadentate diketone
alkali metal picrates
building block
complexation abilities
Molecular Architecture
solution stabilities
size selectivity
tridentate analogue 37
Heptacyclic Terpyridyl Molecular Clefts Methods
lattice receptors
picrate extraction method
tridentate cleft
pentadentate cleft 6
potassium picrate complexes
calcium triflate
1998-03-13 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Molecular_Architecture_2_Synthesis_and_Metal_Complexation_of_Heptacyclic_Terpyridyl_Molecular_Clefts/3708894
Methods are described for the synthesis of a series of
functionalized derivatives of 9-butyl-1,2,3,4,5,6,7,8-octahydroacridine (<b>9</b>), a building block for
several types of highly preorganized host
compounds. A key intermediate is
5-benzylidene-9-butyl-2,3,5,6,7,8-hexahydroacridin-4(1<i>H</i>)-one
(<b>23</b>), which can also be used in the syntheses of torands and
hydrogen-bonding hexagonal lattice
receptors. A tridentate cleft (<b>20</b>), consisting of
2,2‘;6‘,2‘‘-terpyridine imbedded in a heptacyclic
framework, and a corresponding pentadentate diketone (<b>6</b>)
were synthesized from <b>9</b> in five and
seven steps, respectively. The picrate extraction method was used
to estimate the solution stabilities
of alkali metal complexes of heptacyclic terpyridyls <b>6</b> and
<b>20</b>, which was also compared with a
flexible terpyridyl (<b>37</b>). Alkali metal complexes of
both heptacyclic terpyridyls showed relatively
high <i>K</i><sub>s</sub> values, but low size selectivity.
Pentadentate host <b>6</b> binds Na<sup>+</sup> and
K<sup>+</sup> more strongly than
do most hexadentate crown ethers; flexible tridentate analogue
<b>37</b> failed to extract alkali metal
picrates into chloroform. The complexation abilities of
<b>6</b> and <b>20</b> are attributed to enforced
orientation of functional group dipoles toward the center of the
molecular cleft. Sodium and
potassium picrate complexes of pentadentate cleft <b>6</b> were
synthesized (1:1 stoichiometry), and a
2:1 complex of calcium triflate
(<b>6</b><sub>2</sub>·Ca(CF<sub>3</sub>SO<sub>3</sub>)<sub>2</sub>)
was also prepared.