Highly Selective Asymmetric Hydrogenation Using a Three Hindered Quadrant Bisphosphine Rhodium Catalyst

Hoge, Garrett; Wu, Heping; Kissel, William S.; Pflum, Derek A.; Greene, Derek; Bao, Jian

doi:10.1021/ja048496y

Cited by 200 publications

(130 citation statements)

References 7 publications

Supporting

Mentioning

129

Contrasting

Order By: Relevance

“…Mechanistic aspects of catalyzed hydrogenation have previously mainly been studied with Pchirogenic C 2 symmetry diphosphanes, [33,[47][48][49][50][51][52][53][54] with a few examples of dissymmetric ligands having been mentioned. [55] Recently, Vogt's team and our own group have independently described a series of modified P-chirogenic EPHOS ligands 4 (Scheme 3) for catalytic asymmetric hydrogenation and hydroformylation reactions involving rhodium complexes. [56][57][58] These ligands, preparable from ephedrine as starting material by a versatile methodology, offer the potential for modification of the substituents on one or two P-centers.…”

Section: Introductionmentioning

confidence: 99%

Modular P‐Chirogenic Aminophosphane‐Phosphinite Ligands for Rh‐Catalyzed Asymmetric Hydrogenation: A New Model for Prediction of Enantioselectivity

Darcel

Moulin²,

Henry³

et al. 2007

Eur J Org Chem

View full text Add to dashboard Cite

An original series of P-chirogenic aminophosphane-phosphinite (AMPP) ligands has been synthesized from (+)-or (-)-ephedrine in 23 to 61 % overall yields by a versatile threestep methodology. The AMPP ligands, bearing either one or two P-chirogenic centers, were used in the form of rhodium complexes for the catalyzed hydrogenation of α-acetamidocinnamate as a test reaction. Notably, even with AMPP ligands all derived from (+)-ephedrine, variation of the substituent on a P-center allowed the phenylalanine derivatives to be obtained in either (S) or (R) absolute configurations, with ee values ranging from 99 % (S) to 88% (R). The asymmetric induction was analyzed with the aid of X-ray structures of AMPP complexes, and a new model for the enantioselectivity, taking into consideration the boat conformation and the steric and electronic dissymmetries at the dihydride

show abstract

Section: Introductionmentioning

confidence: 99%

Modular P‐Chirogenic Aminophosphane‐Phosphinite Ligands for Rh‐Catalyzed Asymmetric Hydrogenation: A New Model for Prediction of Enantioselectivity

Darcel

Moulin²,

Henry³

et al. 2007

Eur J Org Chem

View full text Add to dashboard Cite

show abstract

“…In so doing, three quadrants in the coordination sphere will be blocked and the only one left free will be situated above the phospholyl plane at the opposite of the [Mn(CO) 2 (PPh 3 )] complexing group. Such geometries are known to favor enantioselection [10]. …”

Section: Resultsmentioning

confidence: 99%

Enantiopure phosphacymantrene‐2‐carboxaldehyde and some of its derivatives

Deschamps

Mathey

2005

Heteroatom Chemistry

View full text Add to dashboard Cite

show abstract

“…Both good selectivity (98% ee) and high turnover numbers of 27,000 were achieved (Eq. 7.12 ) [49] . An Rh -Me -DuPhos complex also provides high enantioselectivity (97.7% ee) although from high catalyst loading ( S / C = 100) [200] .…”

Section: Unsaturated Acids and Their Derivativesmentioning

confidence: 99%

Transition Metal‐Catalyzed Homogeneous Asymmetric Hydrogenation

Gao

Zhang

2010

Catalytic Asymmetric Synthesis

View full text Add to dashboard Cite

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.

show abstract

Highly Selective Asymmetric Hydrogenation Using a Three Hindered Quadrant Bisphosphine Rhodium Catalyst

Cited by 200 publications

References 7 publications

Modular P‐Chirogenic Aminophosphane‐Phosphinite Ligands for Rh‐Catalyzed Asymmetric Hydrogenation: A New Model for Prediction of Enantioselectivity

Modular P‐Chirogenic Aminophosphane‐Phosphinite Ligands for Rh‐Catalyzed Asymmetric Hydrogenation: A New Model for Prediction of Enantioselectivity

Enantiopure phosphacymantrene‐2‐carboxaldehyde and some of its derivatives

Transition Metal‐Catalyzed Homogeneous Asymmetric Hydrogenation

Contact Info

Product

Resources

About