New chiral phospholanes; Synthesis, characterization, and use in asymmetric hydrogenation reactions

Burk, Mark J.; Feaster, John E.; Harlow, Richard L.

doi:10.1016/s0957-4166(00)86109-1

Cited by 270 publications

(114 citation statements)

References 38 publications

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“…24.1) [8][9][10][11][12][13]. Subsequently, these ligands have been successfully employed in numerous enantiomeric catalytic systems [4 a, 5], the most fruitful and prolific being Rh-catalyzed hydrogenations.…”

Section: Early Discoveries and The Breakthrough With Duphos And Bpementioning

confidence: 99%

“…Itaconic acid has been hydrogenated by 25 in various MeOH/H 2 O mixtures, ranging from 9 : 1 to 3 : 97, without variance or loss of enantioselectivity. The three-carbon bridged tridentate ligand (S,S)-Me-11 hydrogenated DMI in 94% ee, albeit with protracted reaction times, whereas the related bidentate ligand (R,R)-Me-7 surprisingly gave only 78% ee [11]. Remarkably, Corma et al have reported the first use Me-DuPhos-based Pt and Au catalysts for the reduction of simple itaconic acid derivatives in high enantioselectivity (3 to 95% ee) and extremely high rates (TOF up to 10 200 h -1 ) [166].…”

Section: Enantioselective Hydrogenation Of Unsaturated Acid and Estermentioning

confidence: 99%

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Enantioselective Hydrogenation: Phospholane Ligands

Cobley¹,

Moran²

2006

The Handbook of Homogeneous Hydrogenation

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The ability to efficiently synthesize enantiomerically enriched materials is of key importance to the pharmaceutical, flavor and fragrance, animal health, agrochemicals, and functional materials industries [1]. An enantiomeric catalytic approach potentially offers a cost-effective and environmentally responsible solution, and the assessment of chiral technologies applied to date shows enantioselective hydrogenation to be one of the most industrially applicable [2]. This is not least due to the ability to systematically modify chiral ligands, within an appropriate catalyst system, to obtain the desired reactivity and selectivity. With respect to this, phosphorus(III)-based ligands have proven to be the most effective.Amongst the hundreds of chiral phosphorus-based ligands developed since the seminal studies of Knowles and Horner [3], only a select few ligand families have had a revolutionary impact on the field. The highly modular chiral C 2 -symmetric phospholane ligands (DuPhos TM and BPE), developed by Burk and coworkers at DuPont, are one such example. As a result, much effort has been directed towards building on this breakthrough discovery and extending both the design and application of this ligand class.In this chapter, we review the growing family of phospholane-based chiral ligands, and specifically examine their applications in the field of enantioselective hydrogenation. In general, this ligand class has found its broadest applicability in the reduction of prochiral olefins and, to a significantly lesser extent, ketones and imines; this is reflected in the composition of the chapter. Several analogous phosphacycle systems have also been included, where appropriate.Whilst trying to be comprehensive, we have also intended to introduce a strong applied flavor to this summary. In the industrial case, catalyst performance is critically judged on overall efficiency, namely catalyst productivity and activity as well as enantioselectivity. As a result, turnover numbers (TONs) and turnover frequencies (TOFs) have been included or calculated whenever possible and meaningful. 773The Handbook of Homogeneous Hydrogenation. Edited by J. G. de Vries and C. J. Elsevier

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Section: Early Discoveries and The Breakthrough With Duphos And Bpementioning

confidence: 99%

Section: Enantioselective Hydrogenation Of Unsaturated Acid and Estermentioning

confidence: 99%

Enantioselective Hydrogenation: Phospholane Ligands

Cobley¹,

Moran²

2006

The Handbook of Homogeneous Hydrogenation

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“…To date, a number of non-biocatalytic, i.e., chemical production procedures yielding (2S,5S)-hexanediol have been developed [30][31][32]. Among these, the catalytic hydrogenation of 2,5-hexanedione appears to be the most efficient approach currently available, and consequently, presents the state-ofthe-art concerning the chemical production route for the compound.…”

Section: Introductionmentioning

confidence: 99%

Application of Material and Energy Flow Analysis in the Early Stages of Biotechnical Process Development – A Case Study

et al. 2010

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Biotechnical technologies are often viewed as generally green processes, since they operate at low temperatures and pressures. However, as shown by various comparative studies of chemical and biotechnical engineering processes, this view cannot be generalized. It is clear that sustainable assessment should be carried out in the early stages of process development, since these stages have a major influence on the economic and ecological performance of processes later at the industrial scale. One option to use as a basis for evaluating the potential advantages to developing a biotechnical process can be a material and energy flow analysis (MEFA) at an early stage. This article provides an understanding of MEFA in general and illustrates its successful application by means of two case studies.

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“…The first examples of chiral analogs were provided by dipamp (1a), chiraphos (2a) [12] and prophos (2b) (Scheme 1). [13] These compounds accommodate centers of chirality, as do bis-(phosphanes) 1b, [14] 3, [15] 4, [16] and 5. [17] The chirality of 1,2-bis(phosphane) 6 [18] is exclusively of the planar variety.…”

Section: Introductionmentioning

confidence: 99%