Improved addition of organolithium reagents to hindered and/or enolisable ketones

Lecomte, Vincent; Stéphan, Elie; Bideau, Franck Le; Jaouen, Gérard

doi:10.1016/s0040-4020(03)00189-3

Cited by 18 publications

(11 citation statements)

References 28 publications

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“…32 The resulting ketone reacts with phenyllithium to give A9 . 33–34 Final treatment of A9 with m CPBA results in epoxide ring fusion at the B-ring to yield A5 .…”

Section: Resultsmentioning

confidence: 99%

A ring-distortion strategy to construct stereochemically complex and structurally diverse compounds from natural products

Huigens

Morrison²,

Hicklin³

et al. 2013

Nature Chem

289

253

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High-throughput screening is the dominant method to identify lead compounds in drug discovery. As such, the makeup of screening libraries will largely dictate the biological targets that can be modulated and the therapeutics that can be developed. Unfortunately, most compound screening collections consist principally of planar molecules with little structural or stereochemical complexity, compounds that do not offer the arrangement of chemical functionality necessary for modulation of many drug targets. Here we describe a novel, general, and facile strategy for the creation of diverse compounds with high structural and stereochemical complexity using readily available natural products as synthetic starting points. We show, through evaluation of chemical properties including fraction of sp3 carbons, ClogP, and the number of stereogenic centers, that these compounds are significantly more complex and diverse than those in standard screening collections, and guidelines are given for the application of this strategy to any suitable natural product.

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“…32 The resulting ketone reacts with phenyllithium to give A9 . 33–34 Final treatment of A9 with m CPBA results in epoxide ring fusion at the B-ring to yield A5 .…”

Section: Resultsmentioning

confidence: 99%

A ring-distortion strategy to construct stereochemically complex and structurally diverse compounds from natural products

Huigens

Morrison²,

Hicklin³

et al. 2013

Nature Chem

289

253

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“…The nucleophilic 2,2′-dilithiobiphenyl adds to the carbonyl groups preferably from the sterically less hindered side, i.e. trans to the isopropyl group in (−)-menthone yielding BIMOL , and trans to the isopropenyl group in (−)-carvone [ 25 – 27 ] yielding BICOL . For (−)-verbenone the sterically less crowded side of the pinene backbone, trans to the geminal dimethyl unit, is preferred yielding BIVOL .…”

Section: Resultsmentioning

confidence: 99%

Control of asymmetric biaryl conformations with terpenol moieties: Syntheses, structures and energetics of new enantiopure C ₂-symmetric diols

Alpagut¹,

Goldfuß²,

Neudörfl³

2008

Beilstein J. Org. Chem.

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New enantiopure, C 2 -symmetric biphenyl-2,2′-diols based on (−)-menthone (BIMOL), (−)-verbenone (BIVOL) and (−)-carvone (BICOL and hydrogenated BIMEOL), are accessible via short, synthetic routes. All diols form intramolecular hydrogen bonds and hence can be employed as chelating ligands for catalyst design, as it demonstrated for the (−)-fenchone based BIFOL. The sense of asymmetry of the biphenyl axes is controlled by the chiral terpene units and is conformationally surprisingly stable. X-ray analyses reveal M biphenyl conformation for BIMOL and P biphenyl conformation for each of BIVOL, BICOL and BIMEOL. The origins of the conformational biphenyl preferences are confirmed by computational ONIOM evaluations of the diols and their diastereomeric conformers. The experimentally observed biphenyl conformations are all energetically preferred, i.e. with 1.3 kcal/mol for (M)-BIMOL, with 5.1 kcal/mol for (P)-BIVOL, with 5.8 kcal/mol for (P)-BICOL, and with 5.4 kcal/mol for (P)-BIMEOL.

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“…Different reaction conditions reported in the literature, some of which for polyanion formation and reaction with some other electrophiles, gave poorer yields and/or complex mixtures. Such is the case for butyllithium in diethyl ether-TMEDA (entry 6), 16 toluene (entry 7), 19 …”

Section: Figurementioning

confidence: 93%

Ultrasound-Promoted Formation of Isopentenyl Alcohol Dianion: Straightforward Synthesis of Perhydrofuro[2,3-b]furans

Alonso¹,

Rodríguez-Fernández²,

Sanchez³

et al. 2010

Synthesis

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Improved addition of organolithium reagents to hindered and/or enolisable ketones

Cited by 18 publications

References 28 publications

A ring-distortion strategy to construct stereochemically complex and structurally diverse compounds from natural products

A ring-distortion strategy to construct stereochemically complex and structurally diverse compounds from natural products

Control of asymmetric biaryl conformations with terpenol moieties: Syntheses, structures and energetics of new enantiopure C ₂-symmetric diols

Ultrasound-Promoted Formation of Isopentenyl Alcohol Dianion: Straightforward Synthesis of Perhydrofuro[2,3-b]furans

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Improved addition of organolithium reagents to hindered and/or enolisable ketones

Cited by 18 publications

References 28 publications

A ring-distortion strategy to construct stereochemically complex and structurally diverse compounds from natural products

A ring-distortion strategy to construct stereochemically complex and structurally diverse compounds from natural products

Control of asymmetric biaryl conformations with terpenol moieties: Syntheses, structures and energetics of new enantiopure C 2-symmetric diols

Ultrasound-Promoted Formation of Isopentenyl Alcohol Dianion: Straightforward Synthesis of Perhydrofuro[2,3-b]furans

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About

Control of asymmetric biaryl conformations with terpenol moieties: Syntheses, structures and energetics of new enantiopure C ₂-symmetric diols