Phosphathiahelicenes: Synthesis and Uses in Enantioselective Gold Catalysis

Aillard, Paul; Voituriez, Arnaud; Dova, D.; Cauteruccio, Silvia; Licandro, Emanuela; Marinetti, Angéla

doi:10.1002/chem.201402822

Cited by 84 publications

(41 citation statements)

References 47 publications

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“…Thus, chromatographically separated endo-76 effectively catalyzes the enantioselective cycloisomerization of N-tethered 1,6-enyne 78 to give bicyclo[4.1.0]heptane 79 with 95% yield and 81% ee, whilst exo-77 remained almost inactive [56] (Scheme 12). Meanwhile, various phosphole-containing ligands were also prepared and screened in similar reactions with success [8,9,57]. Scheme 11.…”

Section: Scheme 11mentioning

confidence: 99%

Helicene-Based Chiral Auxiliaries and Chirogenesis

Hasan

Borovkov

2017

Symmetry

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Helicenes are unique helical chromophores possessing advanced and well-controlled spectral and chemical properties owing to their diverse functionalization and defined structures. Specific modification of these molecules by introducing aromatic rings of differing nature and different functional groups results in special chiroptical properties, making them effective chiral auxiliaries and supramolecular chirogenic hosts. This review aims to highlight these distinct structural features of helicenes; the different synthetic and supramolecular approaches responsible for their efficient chirality control; and their employment in the chirogenic systems, which are still not fully explored. It further covers the limitation, scope, and future prospects of helicene chromophores in chiral chemistry.

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Section: Scheme 11mentioning

confidence: 99%

Helicene-Based Chiral Auxiliaries and Chirogenesis

Hasan

Borovkov

2017

Symmetry

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“…Thus, helicenes can be utilized them a broad range of applications in chiral materials, in the chiral recognition of biomolecules, and in asymmetric synthesis161718192021222324. More specifically, chiral helicene-based trivalent phosphorus ligands are efficient asymmetric inductors in metal-catalyzed asymmetric reactions and show good to excellent enantioselectivities252627282930313233. We hypothesized that novel helicenylphosphine ligands, which induce intramolecular metal-arene interactions, could be used to construct an efficient chiral catalytic system.…”

mentioning

confidence: 99%

Rational Design and Synthesis of [5]Helicene-Derived Phosphine Ligands and Their Application in Pd-Catalyzed Asymmetric Reactions

Yamamoto

Shimizu

Igawa

et al. 2016

Sci Rep

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A series of novel optically active [5]helicene-derived phosphine ligands (L1, with a 7,8-dihydro[5]helicene core structure- and L2, with a fully aromatic [5]helicene core structure) were synthesized. Despite their structural similarities, L1 and L2 exhibit particularly different characteristics in their use as chiral ligands. L1 was highly effective in the asymmetric allylation of indoles with 1,3-diphenylallyl acetate (up to 99% ee), and in the etherification of alcohols (up to 96% ee). In contrast, L2 was highly effective in the stereocontrol of helical chirality in Suzuki–Miyaura coupling (SMC) reaction (up to 99% ee). Density functional theory analysis was employed to propose a model that accounts for the origin of the enantioselectivity in these reactions.

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“…A creative strategy for enantioenriched tetrahydropyridines via enyne cycloisomerization was outlined by Voituriez et al, through the use of a helically chiral gold phosphine catalyst as shown in Scheme 25 [105]. A related class of ligands, phosphathiahelicenes, was also used for this transformation, allowing for even higher enantioselectivities with some substrates [106].…”

Section: Intramolecular Cyclizationsmentioning

confidence: 98%

Enantioselective Gold-Catalyzed Synthesis of Heterocyclic Compounds

Miles

Toste

2015

Topics in Heterocyclic Chemistry

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Asymmetric gold-catalyzed syntheses of a diverse range of heterocycles are described herein. This chapter outlines efforts toward the construction of these molecules via intermolecular, intramolecular, and tandem cyclization strategies. Additionally, asymmetric hydrogenation and epoxidation approaches are detailed. These methodologies generally utilize substrates containing soft, unsaturated carbon-carbon bonds, which can easily interact with the carbophilic gold atom(s). Mostly through the use of bis-or monophosphine ligands, modest to excellent yields and enantioselectivities are obtained for a variety of partially and fully saturated heterocycles. Although steric variation of the phosphine catalyst is the most commonly used strategy for enantioinduction, the use of chiral counteranions has proven useful for more challenging transformations. This chapter includes only examples of syntheses where a chiral gold catalyst is used in the direct formation of the heterocycle; examples of pendant functionalization of an existing heterocycle or chirality transfer from enantioenriched substrate to product are not included.

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Phosphathiahelicenes: Synthesis and Uses in Enantioselective Gold Catalysis

Cited by 84 publications

References 47 publications

Helicene-Based Chiral Auxiliaries and Chirogenesis

Helicene-Based Chiral Auxiliaries and Chirogenesis

Rational Design and Synthesis of [5]Helicene-Derived Phosphine Ligands and Their Application in Pd-Catalyzed Asymmetric Reactions

Enantioselective Gold-Catalyzed Synthesis of Heterocyclic Compounds

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