<i>Carbo</i>-siloles, Part 2: Synthesis and Stereochemical Resolution of a <i>Carbo</i>-silolane Redox Equivalent

Saccavini, Catherine; Tedeschi, Christine; Lepetit, Christine; Yahi, Leila; Pistre, Caroline; Maraval, ValÃ©rie; Chauvin, Rémi

doi:10.1080/10426500902947922

Cited by 6 publications

(3 citation statements)

References 28 publications

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“…Triynediol 8 was previously prepared in excellent yield by bubbling formaldehyde gas into a solution of the dilithium salt of triyne 4 [15]. We found that it can be more conveniently obtained in 95% yield by simply adding solid para-formaldehyde to this solution.…”

Section: Synthesis Of the C 10 Triynediol 8 And Ditosylatementioning

confidence: 92%

“…In order to circumvent this sensitivity, a method for the generation of crude-but-clean 5 was required. It could thus be generated by oxidation of diol 8 with MnO 2 (preactivated by heating overnight at 150 C under vacuum) [9,15]. In THF as solvent, oxidation was not complete (monoaldehyde was always present) and 5 was produced in poor crude yields (<30%).…”

Section: Synthesis Of the C 10 Triynedialmentioning

confidence: 99%

“…MS (DCI/NH 3 ): 4.2.9. 4,7-Dimethoxy-4,7-diphenyl-1,10-bis(tetrahydro-2H-pyran-2-yloxy)deca-2,5,8-triyne (15) To a solution of 13 (3.56 g, 6.92 mmol) in THF (120 mL) under stirring at À78 C was added nbutyllithium (6.1 mL, 15.2 mmol). After 30 min, iodomethane (4.3 mL, 69.2 mmol) and DMSO (4.9 mL, 69.2 mmol) were added at À78 C, and the resulting mixture was allowed to warm slowly to room temperature.…”

Section: Diethyl 47-dimethoxy-47-diphenyldeca-258triynedioate (6a)mentioning

confidence: 99%

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Synthesis and stereochemical resolution of a [6]pericyclynedione: Versatile access to pericyclynediol precursors of carbo-benzenes

Leroyer

Zou

Maraval

et al. 2008

Comptes Rendus. Chimie

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The synthesis of quadrupolar tetraphenyl-carbo-benzene derivatives is envisioned through the corresponding tetraphenyl-tetramethoxy-[6]pericyclynedione last-but-one precursor. The latter was thus prepared in 9 steps and 7% overall yield via the corresponding [6]pericyclynediol, itself obtained by a [8 þ 10] ring formation process between a C 8 octatriyne dinucleophile and a C 10 decatriynedial dielectrophile. In the search for even shorter alternative accesses, the preparation and attempted uses of the corresponding C 10 decatriynediol and diethyl decatriynedioic diester are also described. While the pericyclynediol possesses 14 diastereoisomers proving unseparable, the pericyclynedione possesses five diastereoisomers only that could be resolved by semipreparative HPLC techniques. Reaction of the pericyclynedione with trimethylsilylethynylmagnesium bromide afforded the alkynyl-[6]pericyclyneketol mono-adduct in 22% yield, along with the corresponding [6]pericyclynediol bis-adduct in 43% yield. One of the 14 diastereoisomers of the latter could be separated by column chromatography, and its configuration could be assigned to one of only two possibilities in accordance with the observed number of non-equivalent 1 H and 13 C NMR signals. Since a regioisomer of the dialkynyl-[6]pericyclynediol bis-adduct was shown to undergo ''efficient'' reductive aromatization, these results demonstrate the potential value of the pericyclynedione as a pivotal precursor of p-disubstituted tetraphenyl-carbobenzenes.

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Section: Synthesis Of the C 10 Triynediol 8 And Ditosylatementioning

confidence: 92%

Section: Synthesis Of the C 10 Triynedialmentioning

confidence: 99%

Section: Diethyl 47-dimethoxy-47-diphenyldeca-258triynedioate (6a)mentioning

confidence: 99%

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Synthesis and stereochemical resolution of a [6]pericyclynedione: Versatile access to pericyclynediol precursors of carbo-benzenes

Leroyer

Zou

Maraval

et al. 2008

Comptes Rendus. Chimie

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First Perphenylated carbo‐Oligoacetylenes: An Extension of the Polytriacetylene Family

Rives¹,

Maraval²,

Saffon‐Merceron³

et al. 2012

Chemistry A European J

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The first examples of a novel family of sp-carbon-rich n-π-conjugated oligomers/polymers, namely carbo-mers of polyacetylene, also referred to as "1,4-PTA" isomers of the classical polytriacetylenes (1,2-PTAs), are described in the perphenylated series. The two first representatives proved to be stable in solution, and exhibit a zig-zag arrangement in the crystal state. The third member of the family, isolated in SnCl(2) matrix, proved to be stable in the solid state and was characterized by MALDI-TOF MS, (1)H NMR, CPMAS (13)C NMR, and absorption spectroscopy. An explanation for its reactivity in solution is proposed. The chromophoric properties in the visible region are shown to vary significantly and consistently along the series.

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Siloles

Corey

2011

Advances in Organometallic Chemistry

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Carbo-siloles, Part 2: Synthesis and Stereochemical Resolution of a Carbo-silolane Redox Equivalent

Cited by 6 publications

References 28 publications

Synthesis and stereochemical resolution of a [6]pericyclynedione: Versatile access to pericyclynediol precursors of carbo-benzenes

Synthesis and stereochemical resolution of a [6]pericyclynedione: Versatile access to pericyclynediol precursors of carbo-benzenes

First Perphenylated carbo‐Oligoacetylenes: An Extension of the Polytriacetylene Family

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