2008
DOI: 10.1021/jo801438d
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The Proton Complex of a Diaza-macropentacycle: Structure, Slow Formation, and Chirality Induction by Ion Pairing with the Optically Active 1,1′-Binaphthyl-2,2′-diyl Phosphate Anion

Abstract: The protonation of a sterically crowded [N2S6] macropentacycle (1) with 1 equiv of CF3SO3H in CDCl3 is slow and gives the singly (oo(+) [1 x H](+)) and doubly (o(+)o(+) [1 x 2H](2+)) protonated forms as kinetic products, the i(+)o form of [1 x H](+) being the thermodynamic product. i(+)o [1 x H](+) is C3 helically chiral in the solid state and in solution. The barrier to racemization (DeltaG(double dagger)) of the [1 x H](+) propeller is >71 kJ mol(-1). The ammonium proton is encapsulated in the tetrahedral co… Show more

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Cited by 9 publications
(6 citation statements)
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“…Topological assignments of enantiomers and diastereomers associated with cryptands were best described by Simmons and Park who introduced the term in/out (io) isomerization. This was further supported by Adler et al on amine bridgeheads, and more recently by Chambron where changes in solution dynamics and protonation properties using N 2 S 6 macropentacycle were observed . Macrobicycle L2 can exist as multiple topological isomers (topomers) with different conformations and configurations (Figure ).…”
Section: Introductionmentioning
confidence: 58%
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“…Topological assignments of enantiomers and diastereomers associated with cryptands were best described by Simmons and Park who introduced the term in/out (io) isomerization. This was further supported by Adler et al on amine bridgeheads, and more recently by Chambron where changes in solution dynamics and protonation properties using N 2 S 6 macropentacycle were observed . Macrobicycle L2 can exist as multiple topological isomers (topomers) with different conformations and configurations (Figure ).…”
Section: Introductionmentioning
confidence: 58%
“…This was further supported by Adler et al on amine bridgeheads, 18 and more recently by Chambron where changes in solution dynamics and protonation properties using N 2 S 6 macropentacycle were observed. 19 Macrobicycle L2 can exist as multiple topological isomers (topomers) with different conformations and configurations (Figure 2). Using the io, in/in (ii), or out/ out (oo) nomenclature referencing the location of the lone pairs simplifies the overall descriptors and is intuitive with respect to the overall topology of these systems.…”
Section: ■ Introductionmentioning
confidence: 99%
“…We had shown in earlier work that the reaction of the previously reported macropentacycle 6 with 1 equiv. of CF 3 CO 2 H, CF 3 SO 3 H, or ( S )‐BNPH (( S )‐1,1′‐binaphthyl‐2,2′‐diyl hydrogenphosphate) gave the salts [ 6 H] + ⋅ CF 3 CO 2 − , [ 6 H] + ⋅ CF 3 SO 3 − , or [ 6 H] + ⋅ BNP − , in which the added proton was located on the bridgehead nitrogen atoms in endo conformation, being also bound to the three proximal sulfur atoms of the arylthioether groups, as shown by X‐ray diffraction analysis [17] . The encapsulated proton was in a neutral [NS3] coordination environment, and the other bridgehead nitrogen atom was in exo conformation, which made the molecule unsymmetrical with respect to the plane normal to the N endo ⋅⋅⋅N exo C 3 axis and bisecting the dithioethene bridges.…”
Section: Resultsmentioning
confidence: 99%
“…, in which the added proton was located on the bridgehead nitrogen atoms in endo conformation, being also bound to the three proximal sulfur atoms of the arylthioether groups, as shown by X-ray diffraction analysis. [17] The encapsulated proton was in a neutral [NS3] coordination environment, and the other bridgehead nitrogen atom was in exo conformation, which made the molecule unsymmetrical with respect to the plane normal to the N endo •••N exo C 3 axis and bisecting the dithioethene bridges. We next wondered if 6 could complex soft metal cations in the same coordination sphere as the proton.…”
Section: Complexation Properties Ofmentioning
confidence: 99%
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