Modular chiral ligands: the profiling of the Mandyphos and Taniaphos ligand families

Spindler, Felix; Malan, Christophe; Lotz, Matthias; Kesselgruber, Martin; Pittelkow, Ulrich; Rivas-Nass, Andreas; Briel, Oliver; Blaser, Hans‐Ulrich

doi:10.1016/j.tetasy.2004.06.033

Cited by 63 publications

(26 citation statements)

References 8 publications

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“…Ligands L17 were tested in the standard allylic alkylation and amination reactions of diphenyl allyl acetate with methyl malonate and benzyl amine, respectively. 54]. For details of Bifep please see Chapter 10.…”

Section: Bophoz and Analogsmentioning

confidence: 99%

Bidentate 1,2‐Ferrocenyl Diphosphine Ligands

Blaser¹,

Lotz²

2009

Chiral Ferrocenes in Asymmetric Catalysis

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IntroductionFerrocene as a (at the time rather exotic) backbone for chiral ligands was introduced by Kumada and Hayashi [1], based on Ugis pioneering work related to the synthesis of enantiopure ferrocenes (see Figure 4.1). PPFA as well as BPPFA and BPPFOH were not only the first ferrocene-based ligands but also the first ligands to exhibit both central and planar chirality and they proved to be very effective ligands for a variety of asymmetric transformations. From this starting point, several ligand families with a range of structural variations and types of chiral element have been developed in the last few years, very often starting from Ugi amine. In this chapter we will focus on the application of diphosphines developed over time where the two diphosphine moieties are attached to only one of the cyclopentadienyl (Cp) rings in a 1,2-arrangement. As a consequence these ligands can have a mix of chiral elements: planar chirality due to the ferrocene moiety, central chirality due to stereogenic carbon and/or phosphorus centers and, in one case, even axial chirality. Several recent reviews covering various aspects of ferrocene-based chiral ligands can serve to put the present account into a broader perspective [2]. Furthermore, we have recently summarized the synthetic procedures for most of the ligands described here [3].This chapter is organized according to the five types of arrangement of the two diphosphine moieties at the Cp ring (see Figure 4.2).Type A: Both PR 2 groups are directly attached to the Cp ring.Type B: One PR 2 group is directly attached to the Cp ring, the second PR 2 group is attached to the a position of a side chain.Type C: One PR 2 group is directly attached to the Cp ring, the second PR 2 group is attached to the b position of a side chain.

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Section: Bophoz and Analogsmentioning

confidence: 99%

Bidentate 1,2‐Ferrocenyl Diphosphine Ligands

Blaser¹,

Lotz²

2009

Chiral Ferrocenes in Asymmetric Catalysis

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“…A Rh-Mandyphos catalyst of Solvias/Umicore (see Fig. 37.9) achieved ee-values > 98% with TONs > 20 000 and TOF up to 7700 h -1 (25 8C, 1 bar) for the model substrate MAC [48]. Finally, Eastman's Rh-BoPhoz also achieved ee-values of 97-> 99% for a variety of a-dehydro amino acid derivatives, in some cases with TONs up to 10 000 and very high activities at r.t./*1 bar [49].…”

Section: Various Pilot-and Bench-scale Processes For A-amino Acid Dermentioning

confidence: 99%

Industrial Applications

Blaser¹,

Spindler²,

Thommen³

2006

The Handbook of Homogeneous Hydrogenation

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While hydrogenation is without doubt the most important catalytic methodology for the manufacture of fine chemicals, until now most reactions have been carried out with heterogeneous catalysts. Heterogeneous hydrogenation catalysts have an exceptionally broad applicability for the chemo-and diastereoselective reduction of various functional groups, are convenient to handle, and catalyst separation is usually straightforward [1]. Homogeneous catalysts have found application for a number of special selectivity problems, the most important of which is enantioselective hydrogenation. While this will be the dominant topic of this chapter, a few scattered reports have been made where achiral complexes such as the Wilkinson catalyst, RhCl(Ph 3 P) 3 , or Ru-phosphine complexes have been applied on an industrial scale. In this regard, we will mention three examples [2]: (i) the chemoselective hydrogenation of a,b-unsaturated aldehydes; (ii) the diastereoselective hydrogenation of a tetracycline antibiotic; and (iii) the chemoselective hydrogenation of avermectin derivatives.As already mentioned, the most important industrial application of homogeneous hydrogenation catalysts is for the enantioselective synthesis of chiral compounds. Today, not only pharmaceuticals and vitamins [3], agrochemicals [4], flavors and fragrances [5] but also functional materials [6,7] are increasingly produced as enantiomerically pure compounds. The reason for this development is the often superior performance of the pure enantiomers and/or that regulations demand the evaluation of both enantiomers of a biologically active compound before its approval. This trend has made the economical enantioselective synthesis of chiral performance chemicals a very important topic.Industrial interest in the application of enantioselective catalysts began in earnest during the mid-1960s when the first reports of successful enantioselective transformations with homogeneous metal complexes were published. Within a surprisingly short period, production processes for two small-scale products, l-dopa (hydrogenation) and cilostatin (cyclopropanation) were developed and implemented by 1279The Handbook of Homogeneous Hydrogenation. Edited by J. G. de Vries and C. J. Elsevier

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“…Important examples (see Scheme 1) are (P,P) ligands like TRAP [9][10][11][12][13], Josiphos [14], and particularly the industrially important Xyliphos [15], Taniaphos [16][17][18] and Walphos-type [19] ligands, (P, N) ligands, especially phosphine-oxazolines like, for instance DIPOF [20], and more recently (P, S) ligands like Fesulphos [21].…”

Section: Introductionmentioning

confidence: 99%

Palladium and platinum complexes with planar chiral 1,2-disubstituted ferrocenes containing phosphine and thioether donor groups

Malacea¹,

Routaboul²,

Manoury³

et al. 2008

Journal of Organometallic Chemistry

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Dedicated to the memory of F. Albert Cotton, a caring mentor and a good friend. AbstractThree palladium(II) complexes and four platinum(II) complexes having general formula CpFe{1,2-C 5 H 3 (PPh 2 )(CH 2 SR)}MCl 2 (M = Pd, R = Ph, Et and tBu; M = Pt, R = Ph, Et, tBu and Cy) have been synthesized by reaction of the corresponding CpFe{1,2-C 5 H 3 (PPh 2 )(CH 2 SR)} ligands with PdCl 2 (CH 3 CN) 2 or PtCl 2 (CH 3 CN) 2 . These complexes have been fully characterized in solution and in solid state. In all cases, monomeric square planar complexes were obtained as pure diastereoisomers.

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Modular chiral ligands: the profiling of the Mandyphos and Taniaphos ligand families

Cited by 63 publications

References 8 publications

Bidentate 1,2‐Ferrocenyl Diphosphine Ligands

Bidentate 1,2‐Ferrocenyl Diphosphine Ligands

Industrial Applications

Palladium and platinum complexes with planar chiral 1,2-disubstituted ferrocenes containing phosphine and thioether donor groups

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