Diphosphonites as highly efficient ligands for enantioselective rhodium-catalyzed hydrogenation

Reetz, Manfred T.; Gosberg, Andreas; Goddard, Richard; Kyung, Suk‐Hun

doi:10.1039/a805524f

Cited by 80 publications

(46 citation statements)

References 13 publications

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“…Reetz et al used several backbones, amongst others ferrocene, to prepare chelating diphosphonites and used them in asymmetric Rh-catalyzed hydrogenations of the typical benchmark substrates 4 as well as in conjugate addition of aryl boronic acids. 5 ZanottiGerosa et al also described diphosphonites but they used the para-cyclophane backbone and performed hydrogenation reactions.…”

Section: Introductionmentioning

confidence: 99%

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Coordination chemistry and X-ray studies with novel sterically constrained diphosphonite ligands

et al. 2003

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The coordination of two novel, sterically constrained diphosphonite ligands towards different palladium, platinum and rhodium precursors has been studied. Complexes of this hitherto unexplored class of diphosphonites, based on rigid xanthene backbones, have been characterized by X-ray crystallography as well as by NMR and IR spectroscopy. A short and concise overview is given on the scarce literature on phosphonite related chemistry. Structural differences in the complexes obtained due to steric influences of the ligands are discussed. Ligand 1, bearing 2-tert-butylphenolate groups, led to orthometallated complexes cis-[MCl{1-κ 3 C,P,P}] (M = Pd, Pt) and to trans- [RhCl(CO) (1)]. These complexes were compared with those formed with ligand 2, bearing 2,2Ј-dioxo-3,3Ј-di-tert-butyl-5,5Ј-dimethoxy-1,1Ј-biphenyl groups, preventing orthometallation. The complexes trans-{PdCl 2 (2)], cis-[PtCl 2 (2)] and trans-[RhCl(CO)(2)] were structurally characterized. Valuable data were collected on chemical shifts, Pt-P coupling constants, as well as CO stretch frequencies of Rh-CO complexes as important tools for structural characterization of such complexes. IntroductionProgress and development of homogeneous catalysis is very much related and dependent on the synthesis and availability of ligands. In recent years a number of powerful new ligand classes have emerged, most of which are chelating phosphorusbased compounds 1 such as phosphines 2 or phosphites.3 Phosphonites however have been widely neglected and only very recently a few examples were reported. Reetz et al. used several backbones, amongst others ferrocene, to prepare chelating diphosphonites and used them in asymmetric Rh-catalyzed hydrogenations of the typical benchmark substrates 4 as well as in conjugate addition of aryl boronic acids.5 ZanottiGerosa et al. also described diphosphonites but they used the para-cyclophane backbone and performed hydrogenation reactions.6 Pringle andco-workers used binaphthol-derived mono-and bidentate phosphonites for conjugate additions of diethyl zinc to enones. 7 The same monophosphonites were used by Claver and Pringle in asymmetric hydrogenations.8 Scharf and co-workers used the monodentate phosphonites based on TADDOL as the chiral auxiliary for the rhodum-catalyzed hydrosilylation of ketones.9 Börner and co-workers have published on the use of both monodentate and bidentate phosphonite ligands in the hydroformylation of alkenes, with varying results.10 Finally the Reetz group, in line with their earlier work, prepared phosphite-phosphonite bidentate ligands but no applications in catalysis were reported so far. 11During recent years xanthene-based chelating ligands have been introduced and extensively used in transition metal catalyzed C-C bond forming reactions.12 These backbones provide a unique combination of rigidity and P-P distance in such a way, that specific, large bite-angle coordination modes are supported. Additionally interaction of the central oxygen atom in the backbone with a metal atom coordinated is possible...

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Section: Introductionmentioning

confidence: 99%

“…28 The groups of Schmutzler and Börner have prepared a new calix [4]arenebased diphosphonite, starting from 6-chlorodibenzo-1-oxa-σ 3 λ 3 -phosphorine as the P-building block. They have made notice of the related PtCl 2 complex, for which the 31 P NMR spectrum showed two doublets (due to stereogenic P-atoms) and coupling constants J Pt-P of around 5060 Hz.…”

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Coordination chemistry and X-ray studies with novel sterically constrained diphosphonite ligands

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“…4) appear to be particularly effective, e.g. in the hydrogenation of ole®ns [13]. Since 4 is easily accessible, it competes well with other ligands known in the literature (Scheme 9) [1].…”

Section: New Chiral Diphosphonite Ligandsmentioning

confidence: 97%

“…Other recent work in our laboratories has shown that diphosphonites 4 and 18±20 composed of an achiral backbone and a chiral P/O heterocycle derived from dinaphthol (or chiral 1,2-diols) constitute a remarkably ef®cient class of ligands [13,32]. The virtues include simplicity of preparation and high enantioselectivity in a variety of different reactions (Scheme 8).…”

Section: New Chiral Diphosphonite Ligandsmentioning

confidence: 99%

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Strategies for the development of enantioselective catalysts

Reetz¹

1999

Pure and Applied Chemistry

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Novel C 2 -symmetric diiminosphosphoranes and diketimines are useful ligands for Pd-and Cu-catalyzed C±C bond forming reactions, Angermund's molecular modeling based on accessible molecular surface serving as a guide in predicting catalyst activity. The ®rst highly enantioselective diphosphites as ligands in Rh-catalyzed hydrogenation are also described, the selectivity principle being based on in situ selection of conformational enantiomers. Finally, a systematic study of chiral diphosphonites reveals that ferrocene-based derivatives are ideal in hydrogenation and certain conjugate addition reactions. These methods are compared to biocatalytic strategies based on the creation of enantioselective biocatalysts by in vitro evolution, a rational process which is independent of the catalyst structure or mechanism.

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Catalysts for Fine Chemical Synthesis

Roberts¹,

Poignant²

2002

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The science of biotransformations has been investigated since the days of Pasteur [1] . However, progress in the use of enzymes and whole cells in synthetic organic chemistry was relatively slow until the 1950s, when the use of microorganisms to modify the steroid nucleus was studied in industry and academic laboratories [2] . Thus conversions such as the transformation of 17a-acetoxy-11deoxycortisol into cortisol (hydrocortisone) (1), using the microorganismCurvularia lunata to introduce the 11b-hydroxy group directly, helped to revive interest in the application of biological catalysis to problems in synthetic organic chemistry. The momentum was continued by Charles Sih, J. Bryan Jones, George Whitesides and others, until, by the mid-1980s, biocatalysis

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Diphosphonites as highly efficient ligands for enantioselective rhodium-catalyzed hydrogenation

Cited by 80 publications

References 13 publications

Coordination chemistry and X-ray studies with novel sterically constrained diphosphonite ligands

Coordination chemistry and X-ray studies with novel sterically constrained diphosphonite ligands

Strategies for the development of enantioselective catalysts

Catalysts for Fine Chemical Synthesis

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