A Chiral 1,2-Bisphospholane Ligand with a Novel Structural Motif: Applications in Highly Enantioselective Rh-Catalyzed Hydrogenations

Tang, Wenjun; Zhang, Xumu

doi:10.1002/1521-3773(20020503)41:9<1612::aid-anie1612>3.0.co;2-h

Cited by 302 publications

(128 citation statements)

References 25 publications

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“…A large number of catalysts, mostly Rh -phosphine catalysts, have been demonstrated to give very good enantioselectivities on the standard substrates. High turnover numbers up to 10,000 have been achieved with Ph -BPE [52] , TangPhos [84] , and 103 [93] for α -arylenamides. In the case of β -substituted substrates, E/Z mixtures can also be reduced with high enantioselectivities using BPE [143] and TangPhos [84] .…”

Section: Asymmetric Hydrogenation Of β -Dehydroamino Acidsmentioning

confidence: 99%

Transition Metal‐Catalyzed Homogeneous Asymmetric Hydrogenation

Gao

Zhang

2010

Catalytic Asymmetric Synthesis

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INTRODUCTIONAmong all the catalytic asymmetric methodologies to chiral compounds, homogenous transition metal -catalyzed asymmetric hydrogenation plays a particularly important role [1] . Its highly effi cient, environmental friendly, and cost -effective natures have undoubtly made it one of the most studied methodologies during the past 40 years. As a result, the vast number of catalytic systems developed has also had a signifi cant impact on other areas of asymmetric catalysis [2] . More signifi cantly, the achievements from academia research on asymmetric hydrogenation were frequently acknowledged with industrial applications, which, in turn, provide an important driving force for its basic research [3] .Hundreds of catalytic systems have been developed since the seminal discoveries from Knowles and Sabacky [4] , Kagan and Dang [5] , and Horner et al. [6] . In many cases, series of chiral catalysts were developed based on the similar scaffolds and were prepared for the same reactions. Although these analogous ligands are more likely prepared for the purpose of patent protection other than academic curiosity, they indeed provide us an excellent opportunity to compare, evaluate, and study every aspect of the catalysts in asymmetric hydrogenation. In the meantime, a large number of prochiral unsaturated compounds have been successfully hydrogenated with excellent enantioselectivities. Practical applications with very low catalyst loadings and complex substrate structures have continued to emerge since the publication of the last edition of this book.

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Section: Asymmetric Hydrogenation Of β -Dehydroamino Acidsmentioning

confidence: 99%

Transition Metal‐Catalyzed Homogeneous Asymmetric Hydrogenation

Gao

Zhang

2010

Catalytic Asymmetric Synthesis

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“…In the literature, the synthesis of a few optically active P-chiral heterocyclic ligands was described and the transition metal complexes of these P(III)-compounds were used as catalysts mainly in enantioselective hydrogenation reactions [11,13,16,18,21,[28][29][30][31][32]. There are only a few examples for P-heterocyclic ligands that were used in hydroformylation [5].…”

Section: Introductionmentioning

confidence: 99%

A study on the optical resolution of 1-isopropyl-3-methyl-3-phospholene 1-oxide and its use in the synthesis of borane and platinum complexes

Bagi

Juhász

Timári

et al. 2015

Journal of Organometallic Chemistry

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A 1-isopropyl-3-phospholene 1-oxide was prepared and the two enantiomers were isolated from the racemate by resolution using optically active TADDOL derivatives or the acidic Ca 2+ salts of (-)-O,O-diaroyl-(2R,3R)-tartaric acids. The single crystal X-ray structure of the 2 1-isopropyl-3-phospholene oxide -spiro-TADDOL 1:2 associate revealed the mode of binding between the host and guest molecules. The role of the interactions between the three molecules was supported not only by the contact data, but also force field and semiempirical calculations. Beside X-ray analysis, the absolute configuration of the P-stereogenic center was also determined on the basis of CD spectroscopy and high level quantum chemical calculations. The racemic and optically active 1-isopropyl-3-phospholenes obtained after deoxygenation were converted to the corresponding borane complexes and Pt(II) complexes.Stereostructure of the latter species was evaluated by high level quantum chemical calculations and the Pt complexes were tested as catalysts in the hydroformylation of styrene.

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“…[10] Higher enantioselectivities were obtained with chiral phosphine ligands like DuPHOS, BPE, [11,12,13] CDP, [14] BICP, [15] Binaphane, [16] , DIOP analogues, [17,18] bdpmi, [19] PennPhos, [20] aminophosphine BDPAB, [21] bisphosphinite spirOP [22] and TangPhos. [23,24] Bidentate ligands which can chelate rhodium were used in all these studies with the majority being chiral diphosphines. The limited number of studies on the asymmetric hydrogenation of a-arylenamides suggests that this is a class of substrates which is more difficult to hydrogenate with high enantioselectivity.…”

Section: Introductionmentioning

confidence: 99%