Reversible formation of a planar chiral ferrocenylboroxine and its supramolecular structure

Pakkirisamy Thilagar, Jiawei Chen, Roger Lalancette, Frieder Jaekle

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

The boronic acid (pS)-1,2-NpFcB(OH) 2 (1) was obtained by treatment of the lithiated species (pS)-1,2-NpFcLi with B(O iPr) 3, followed by acidic workup; subsequent dehydration gave the enantiomerically pure boroxine [(pS)-1,2-NpFcBO] 3 (2) in 49% isolated yield. Multinuclear and 2D NMR spectroscopies, single-crystal X-ray diffraction, and elemental analysis served to confirm the structure of 2. In the solid-state structure, all three of the naphthyl groups point in one direction and all of the ferrocenyl moieties are placed on the opposite face of the boroxine ring, which is also the preferred conformation in solution according to a 1H, 1H-NOESY experiment. Cyclic voltammetry revealed three separate reversible oxidation events, which suggests significant communication between the ferrocenyl moieties. These redox processes experience a cathodic shift upon addition of 4-dimethylaminopyridine (DMAP) as a Lewis base. The six-membered ring is opened upon treatment with hot CHCl 3/MeOH to form the methoxy species (pS)-1,2-NpFcB(OH)(OMe) (3), which can be converted back to the cycle 2 by dissolution in wet CHCl 3, followed by column chromatography on silica gel.

Original languageEnglish (US)
Pages (from-to)6734-6741
Number of pages8
JournalOrganometallics
Volume30
Issue number24
DOIs
StatePublished - Dec 26 2011

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Lewis Bases
Boronic Acids
Point groups
Column chromatography
Silica Gel
Dehydration
X ray diffraction analysis
Nuclear magnetic resonance spectroscopy
Cyclic voltammetry
Conformations
Dissolution
Single crystals
Oxidation
Lewis base
rings
Communication
silica gel
chromatography
Chemical analysis
dehydration

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

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title = "Reversible formation of a planar chiral ferrocenylboroxine and its supramolecular structure",
abstract = "The boronic acid (pS)-1,2-NpFcB(OH) 2 (1) was obtained by treatment of the lithiated species (pS)-1,2-NpFcLi with B(O iPr) 3, followed by acidic workup; subsequent dehydration gave the enantiomerically pure boroxine [(pS)-1,2-NpFcBO] 3 (2) in 49{\%} isolated yield. Multinuclear and 2D NMR spectroscopies, single-crystal X-ray diffraction, and elemental analysis served to confirm the structure of 2. In the solid-state structure, all three of the naphthyl groups point in one direction and all of the ferrocenyl moieties are placed on the opposite face of the boroxine ring, which is also the preferred conformation in solution according to a 1H, 1H-NOESY experiment. Cyclic voltammetry revealed three separate reversible oxidation events, which suggests significant communication between the ferrocenyl moieties. These redox processes experience a cathodic shift upon addition of 4-dimethylaminopyridine (DMAP) as a Lewis base. The six-membered ring is opened upon treatment with hot CHCl 3/MeOH to form the methoxy species (pS)-1,2-NpFcB(OH)(OMe) (3), which can be converted back to the cycle 2 by dissolution in wet CHCl 3, followed by column chromatography on silica gel.",
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Reversible formation of a planar chiral ferrocenylboroxine and its supramolecular structure. / Thilagar, Pakkirisamy; Chen, Jiawei; Lalancette, Roger; Jaekle, Frieder.

In: Organometallics, Vol. 30, No. 24, 26.12.2011, p. 6734-6741.

Research output: Contribution to journalArticle

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T1 - Reversible formation of a planar chiral ferrocenylboroxine and its supramolecular structure

AU - Thilagar, Pakkirisamy

AU - Chen, Jiawei

AU - Lalancette, Roger

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N2 - The boronic acid (pS)-1,2-NpFcB(OH) 2 (1) was obtained by treatment of the lithiated species (pS)-1,2-NpFcLi with B(O iPr) 3, followed by acidic workup; subsequent dehydration gave the enantiomerically pure boroxine [(pS)-1,2-NpFcBO] 3 (2) in 49% isolated yield. Multinuclear and 2D NMR spectroscopies, single-crystal X-ray diffraction, and elemental analysis served to confirm the structure of 2. In the solid-state structure, all three of the naphthyl groups point in one direction and all of the ferrocenyl moieties are placed on the opposite face of the boroxine ring, which is also the preferred conformation in solution according to a 1H, 1H-NOESY experiment. Cyclic voltammetry revealed three separate reversible oxidation events, which suggests significant communication between the ferrocenyl moieties. These redox processes experience a cathodic shift upon addition of 4-dimethylaminopyridine (DMAP) as a Lewis base. The six-membered ring is opened upon treatment with hot CHCl 3/MeOH to form the methoxy species (pS)-1,2-NpFcB(OH)(OMe) (3), which can be converted back to the cycle 2 by dissolution in wet CHCl 3, followed by column chromatography on silica gel.

AB - The boronic acid (pS)-1,2-NpFcB(OH) 2 (1) was obtained by treatment of the lithiated species (pS)-1,2-NpFcLi with B(O iPr) 3, followed by acidic workup; subsequent dehydration gave the enantiomerically pure boroxine [(pS)-1,2-NpFcBO] 3 (2) in 49% isolated yield. Multinuclear and 2D NMR spectroscopies, single-crystal X-ray diffraction, and elemental analysis served to confirm the structure of 2. In the solid-state structure, all three of the naphthyl groups point in one direction and all of the ferrocenyl moieties are placed on the opposite face of the boroxine ring, which is also the preferred conformation in solution according to a 1H, 1H-NOESY experiment. Cyclic voltammetry revealed three separate reversible oxidation events, which suggests significant communication between the ferrocenyl moieties. These redox processes experience a cathodic shift upon addition of 4-dimethylaminopyridine (DMAP) as a Lewis base. The six-membered ring is opened upon treatment with hot CHCl 3/MeOH to form the methoxy species (pS)-1,2-NpFcB(OH)(OMe) (3), which can be converted back to the cycle 2 by dissolution in wet CHCl 3, followed by column chromatography on silica gel.

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