Diastereomeric P∗-chiral diamidophosphites with terpene fragments in asymmetric catalysis

Gavrilov, K. N.; Benetsky, Eduard B.; Grishina, Tatiana B.; Zheglov, Sergey V.; Rastorguev, E. A.; Petrovskii, P. V.; Macaev, Fliur; Davankov, V. A.

doi:10.1016/j.tetasy.2007.10.022

Cited by 19 publications

(5 citation statements)

References 40 publications

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“…18,26- 30 Ligands 4 and 5 are rather stable in air and capable of prolong storage under a dry atmosphere. Similarly to re lated compounds 1-3 (see , (S C ,R P ) 4, (R C ,S P ) 4 are typical chelating agents by their coor dination compounds.…”

Section: Resultsmentioning

confidence: 99%

Diastereomeric P-mono- and P,P*-bidentate diamidophosphite ligands based on 1,4:3,6-dianhydro-d-mannitol in asymmetric metallocomplex catalysis

et al. 2008

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Synthesis of diastereomeric mono and bidentate diamidophosphites bearing P* stereo centers and phosphabicyclo[3.3.0]octane backbone and their coordination with rhodium(I) and palladium(II) are considered. Their use in Rh catalyzed asymmetric allylation allowed one to achieve 87% ee values and the use in Rh catalyzed asymmetric hydrogenation gave up to 98% ee.Asymmetric metallocomplex catalysis represents a highly efficient methodology for the preparation of valu able enantiomerically pure organic and organoelement compounds. 1-3 Chemical and optical yields close to quan titative are achieved in enantioselective catalytic transfor mations due to the most careful optimization of various reaction parameters. The key unit of the optimization process is the correct choice of the ligand group and ratio nal design of each ligand from this ligand group. 4 Among phosphorus containing ligands, the predominant position is occupied by P,P bidentate ligands. However, in the recent time many researchers use more electron with drawing compounds of the phosphite type. The latter are especially attractive by simplicity of their preparation from accessible precursors and stability to oxidative destruc tion. In addition, they are characterized by the pronounced π acidity and low cost. 5-10 At the same time, only several promising P*,P* bidentate ligands of the phosphite type bearing stereogenic phosphorus atoms are described. 11-13 This is rather surprising, because it is well known 2 that ligands with asymmetric donor atoms are excellent stereoselectors.It is worth noting that cheap chiral diols bearing several C* stereocenters are a very abundant pool for the synthesis of P,P bidentate phosphites. 4-10 In particular, a series of phosphite and phosphinite ligands 1-3 based on 1,4:3,6 dianhydro D mannitol (see below) were success fully used in selected reactions of asymmetric hydrogena tion and allylic substitution. 14-17 R = R´ = H (a); R = Me, R´ = H (b); R = R´ = Bu t (c)

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Section: Resultsmentioning

confidence: 99%

Diastereomeric P-mono- and P,P*-bidentate diamidophosphite ligands based on 1,4:3,6-dianhydro-d-mannitol in asymmetric metallocomplex catalysis

et al. 2008

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“…The palladium-catalyzed allylic substitution has also been used as a benchmark reaction for testing a variety of phosphorusbased monodentate ligands (see below and Ref. [331][332][333][334]).…”

Section: Palladium-catalyzed Allylic Substitution Reactionsmentioning

confidence: 99%

Phosphoramidites: Privileged Ligands in Asymmetric Catalysis

Teichert¹,

Feringa²

2010

Angew Chem Int Ed

638

340

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Asymmetric catalysis with transition-metal complexes is the basis for a vast array of stereoselective transformations and has changed the face of modern synthetic chemistry. Key to this success has been the design of chiral ligands to control the regio-, diastereo-, and enantioselectivity. Phosphoramidites have emerged as a highly versatile and readily accessible class of chiral ligands. Their modular structure enables the formation of ligand libraries and easy fine-tuning for a specific catalytic reaction. Phosphoramidites frequently show exceptional levels of stereocontrol, and their monodentate nature is essential in combinatorial catalysis, where a ligand-mixture approach is used. In this Review, recent developments in asymmetric catalysis with phosphoramidites used as ligands are discussed, with a focus on the formation of carbon-carbon and carbon-heteroatom bonds.

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“…Zudem diente die Pd-katalysierte allylische Substitution als Testreaktion zur Untersuchung verschiedener einzähniger Phosphorliganden (siehe unten und Liz. [331][332][333][334] [336,337] allerdings konnten keine wesentlichen Verbesserungen der zuvor beschriebenen Methode erreicht werden. Die Pd-katalysierten allylischen Substitutionen von Cyclohexenyl-und Cyclopentenylacetat mit verschiedenen Binaphthyl-und Biphenol-PhosphoramiditLiganden L2 und L16 (siehe Abbildungen 4 und 5) verliefen mit nur schlechten Enantioselektivitäten.…”

Section: Palladiumkatalysierte Allylische Substitutionenunclassified

Phosphoramidite: privilegierte Liganden in der asymmetrischen Katalyse

2010

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Die asymmetrische Katalyse mit Übergangsmetallkomplexen ist die Grundlage unzähliger stereoselektiver Umwandlungen und hat damit das Bild der modernen Synthesechemie gewandelt. Der Schlüssel zum Erfolg war die Entwicklung chiraler Liganden zur Kontrolle der Regio‐, Diastereo‐ und Enantioselektivität. Dabei haben sich Phosphoramidite als eine äußerst vielseitige und leicht zugängliche Klasse von chiralen Liganden erwiesen. Ihre modulare Struktur ermöglicht die Herstellung von Ligandenbibliotheken und erleichtert die Feinabstimmung für eine bestimmte katalytische Reaktion. Phosphoramidite bewirken oft außerordentlich hohe Stereoselektivitäten, und ihre einzähnige Natur ist in der kombinatorischen Katalyse, die gemischte Liganden verwendet, unverzichtbar. In diesem Aufsatz werden neue Entwicklungen in der asymmetrischen Katalyse mit Phosphoramiditen diskutiert, wobei der Schwerpunkt auf der Bildung von Kohlenstoff‐ Kohlenstoff‐ und Kohlenstoff‐Heteroatom‐Bindungen liegt.

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Diastereomeric P∗-chiral diamidophosphites with terpene fragments in asymmetric catalysis

Cited by 19 publications

References 40 publications

Diastereomeric P-mono- and P,P*-bidentate diamidophosphite ligands based on 1,4:3,6-dianhydro-d-mannitol in asymmetric metallocomplex catalysis

Diastereomeric P-mono- and P,P*-bidentate diamidophosphite ligands based on 1,4:3,6-dianhydro-d-mannitol in asymmetric metallocomplex catalysis

Phosphoramidites: Privileged Ligands in Asymmetric Catalysis

Phosphoramidite: privilegierte Liganden in der asymmetrischen Katalyse

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Diastereomeric P∗-chiral diamidophosphites with terpene fragments in asymmetric catalysis

Cited by 19 publications

References 40 publications

Diastereomeric P*-mono- and P*,P*-bidentate diamidophosphite ligands based on 1,4:3,6-dianhydro-d-mannitol in asymmetric metallocomplex catalysis

Diastereomeric P*-mono- and P*,P*-bidentate diamidophosphite ligands based on 1,4:3,6-dianhydro-d-mannitol in asymmetric metallocomplex catalysis

Phosphoramidites: Privileged Ligands in Asymmetric Catalysis

Phosphoramidite: privilegierte Liganden in der asymmetrischen Katalyse

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Diastereomeric P-mono- and P,P*-bidentate diamidophosphite ligands based on 1,4:3,6-dianhydro-d-mannitol in asymmetric metallocomplex catalysis

Diastereomeric P-mono- and P,P*-bidentate diamidophosphite ligands based on 1,4:3,6-dianhydro-d-mannitol in asymmetric metallocomplex catalysis