2-Phospha[3]ferrocenophanes with Planar Chirality: Synthesis and Use in Enantioselective Organocatalytic [3 + 2] Cyclizations

Voituriez, Arnaud; Panossian, Armen; Fleury‐Brégeot, Nicolas; Retailleau, Pascal; Marinetti, Angéla

doi:10.1021/ja806060a

Cited by 261 publications

(90 citation statements)

References 31 publications

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“…The disconnections of the C3 0 -C7 0 and C4 0 -C6 0 bonds of 25 led to the homopropargyl alcohol 26, which could undergo our newly developed Rh-catalysed intramolecular [ ARTICLE reactions. In this way, our retrosynthetic analysis was traced back to the preparation of enone 27, which could be made from commercially available 5,8-dimethoxy-3,4-dihydronaphthalen-1(2H)-one (28) (Fig. 5).…”

Section: Resultsmentioning

confidence: 99%

Asymmetric total synthesis of (−)-lingzhiol via a Rh-catalysed [3+2] cycloaddition

et al. 2014

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The development of efficient reactions for the one-pot construction of bicyclic ring systems bearing two quaternary carbon centres at their bridgehead positions represents a significant challenge to synthetic chemistry. The development of new methods capable of overcoming this challenge is highly desirable, because this motif can be found in a wide range of natural products with significant biological activities. Herein, we report an efficient [3 þ 2] cycloaddition reaction between an enal and an alleno rhodium species, which was generated in situ from the corresponding enynol via a retro metal-propargylation reaction, to give [3.3.0] and [3.4.0] bicyclic systems bearing two quaternary atoms at their bridgehead positions. The developed chemistry has been successfully applied to the asymmetric total synthesis of natural product ( À )-lingzhiol (4) for the first time in 17 steps.

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Section: Resultsmentioning

confidence: 99%

Asymmetric total synthesis of (−)-lingzhiol via a Rh-catalysed [3+2] cycloaddition

et al. 2014

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“…Part of this work has been reported previously as a preliminary communication. [11] Results and Discussion…”

Section: Introductionmentioning

confidence: 99%

“…In our search for new phosphine organocatalysts, we targeted 2-phospha [3]ferrocenophane derivatives, with either stereogenic carbons (I) [12] or planar chirality (II), [11] since these ferrocenophane scaffolds display some peculiar structural features that are, a priori, amenable to enantioselective organocatalysis.…”

Section: Introductionmentioning

confidence: 99%

“…Phosphines 16a-c have been described in our previous communication. [11] The [Cy]-Et 3 Si-FerroPHANE 16d and [Cy]-Me 2 PhSi-FerroPHANE 16e are orange oils which have been purified by column chromatography and fully characterized. Unlike FerroPHANE 16c which hardly oxidizes in solution at room temperature (< 5% oxidation after 24 h in CDCl 3 solution, in air), FerroPHANEs 16d and 16e are moderately airsensitive compounds which are better handled and stored under inert atmospheres.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis of Chiral 2‐Phospha[3]ferrocenophanes and their Behaviour as Organocatalysts in [3+2] Cyclization Reactions

et al. 2009

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Planar chiral 2-phospha[3]ferrocenophanes have been prepared via a stereoselective three-step synthesis. The key step is the lithiation of the 1,1'-di-A C H T U N G T R E N N U N G substituted ferrocene 11 bearing (S)-2-(methoxymethyl)pyrrolidines as the chiral ortho-directing groups. The diastereoselectivity of these reactions has been mastered by an appropriate choice of the metallating agent, so as to afford a suitable access to C 2 -symmetrical, tetrasubstituted ferrocenes. These compounds have been converted into the enantiomerically pure 2-phospha[3]-ferrocenophanes 16, via the corresponding acetates and their reactions with primary phosphines. Phosphines 16 have been used as nucleophilic catalysts in model cyclization reactions. Unlike 2-phospha[3]-ferrocenophanes with stereogenic acarbons, the planar chiral derivatives 16 proved to be suitable catalysts for these processes. Thus, for instance, phosphine 16c successfully promotes the enantioselective [3 + 2] annulations of allenes and enones into functionalized cyclopentenes (ees up to 96%). Among others, spirocyclic derivatives have been obtained in good yields and ees in the range 77-85%. The robustness of this catalyst has been demonstrated by recycling experiments.

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“…The synthesis of other spirocyclic systems similar to 179 was attempted obtaining, in general, very good yields and enantioselectivities (88% and 80% ee). 85 As it was described above for Lewis acids, organocatalysts can also control the regioselectivity of the 1,3-DC. Although a chiral phosphane promoted the formation of the g-adducts in the presence of a,b-unsaturated ketones (chalcones), the (diphenylphosphino) methylglycine derivative 168 (10-100 mol%, Figure 11) induced a completely opposite regiochemistry, favouring the generation of the cycloadduct a-181 at -25 ºC in toluene in short reaction times (Scheme 40, reaction b).…”

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confidence: 96%

Metal complexes versus organocatalysts in asymmetric 1,3-dipolar cycloadditions

Nájera¹,

Sansano²,

Yus³

2010

J. Braz. Chem. Soc.

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Neste review apresentamos uma comparação entre reações de cicloadição 1,3-dipolar catalizadas por ácido de Lewis com as organo catalizadas, com ênfase na síntese enantiosseletiva de sistemas hetero ou carbocíclicos de cinco membros. Essas reações exibem características interessantes, mas a mais importante é a formação de até quatro centro estereogênicos em apenas uma etapa de reação.In this review, a comparison between the Lewis acid catalysed and organocatalysed 1,3-dipolar cycloaddition is presented with special focus on the enantioselective synthesis of five-membered hetero-or carbocyclic systems, is described. These reactions exhibit very interesting features, but the most important one is the generation of up to four stereogenic centres in only one reaction step.

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2-Phospha[3]ferrocenophanes with Planar Chirality: Synthesis and Use in Enantioselective Organocatalytic [3 + 2] Cyclizations

Cited by 261 publications

References 31 publications

Asymmetric total synthesis of (−)-lingzhiol via a Rh-catalysed [3+2] cycloaddition

Asymmetric total synthesis of (−)-lingzhiol via a Rh-catalysed [3+2] cycloaddition

Synthesis of Chiral 2‐Phospha[3]ferrocenophanes and their Behaviour as Organocatalysts in [3+2] Cyclization Reactions

Metal complexes versus organocatalysts in asymmetric 1,3-dipolar cycloadditions

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