Asymmetric Reactions Catalyzed by Chiral Metal Complexes. XLV. Efficient Preparation of Optically Active (S)-(-)-3-Methyl-.GAMMA.-butyrolactone by Catalytic Asymmetric Hydrogenation Using Chiral N-Substituted Pyrrolidinebisphosphine Rhodium Complexes.

Takeda, Hideo; Tachinami, Takeshi; Hosokawa, S.; Aburatani, Masakazu; Inoguchi, Kiyoshi; Achiwa, Kazuo

doi:10.1248/cpb.39.2706

Cited by 11 publications

(12 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…25 ± 28 The introduction of highly polar substituents into the aromatic fragments of the (R)-PROPHOS (34a) and (S,S)-CHIRAPHOS (36) ligands gave rise to water-soluble derivatives. The reaction of chiral ligand 36 with oleum produced the tetrasulfonated analogue of (S,S)-CHIRAPHOS (37). Under the same conditions, sulfonation of bisphosphine 34a proceeded much more slowly and with lower selectivity.…”

Section: Organophosphorus Ligands Based On Hydroxy Acids 1 Synthesis ...mentioning

confidence: 99%

“…36 Later on, various derivatives of bisphosphinopyrrolidines 61, viz., amides 62, carbamides 63 and carbamates 64a,b, were prepared. 37 The synthesis of bisphosphines 65 ± 69 containing various combinations of cyclohexyl and phenyl groups at the phosphorus atoms offers wide possibilities in the design of pyrrolidine-type ligands. 38,39 Multistep transformations of 4-hydroxy-L-proline (59) produced phosphine oxides 70 and 71.…”

Section: Organophosphorus Ligands Based On Amino Acids 1 Synthesis Of...mentioning

confidence: 99%

“…The use of these catalysts led to an increase in the enantioselectivity to 77% at normal H 2 pressure, whereas hydrogenation catalysed by the Rh(I) complexes with ligands 62a ± e and 64a,b proceeded only under an H 2 pressure of 30 atm, the enantiomeric purities being 43% ± 64% and 53% ± 66%, respectively. 37 The introduction of the p-Me 2 N group into the benzene ring of the BPPM ligand (compounds 76e ± g) led to an increase in the activity and stereoselectivity of the Rh catalyst for the hydrogenation of dimethyl itaconate. The best results (ee = 93%, the conversion was 100%) were achieved in the presence of the Rh(I) complex with ligand 76f (for comparison, hydrogenation catalysed by the complex with unmodified BPPM afforded the product with an ee of 5% and a conversion of 36%).…”

Section: Use In Asymmetric Synthesismentioning

confidence: 99%

See 2 more Smart Citations

Natural compounds in the synthesis of chiral organophosphorous ligands

Толстиков¹,

Khlebnikova²,

Tolstikova³

et al. 2003

Russ. Chem. Rev.

View full text Add to dashboard Cite

Methods for the synthesis of chiral organophosphorus Methods for the synthesis of chiral organophosphorus compounds based on natural optically active compounds compounds based on natural optically active compounds (hydroxy acids, amino acids and their derivatives, mono-and (hydroxy acids, amino acids and their derivatives, mono-and disaccharides, mono-and diterpenoids, steroids) are discussed. disaccharides, mono-and diterpenoids, steroids) are discussed. Particular attention is given to the synthesis of bisphosphines and Particular attention is given to the synthesis of bisphosphines and bisphosphinites. These compounds serve as ligands for transition bisphosphinites. These compounds serve as ligands for transition metal complexes, which catalyse asymmetric hydrogenation. Data metal complexes, which catalyse asymmetric hydrogenation. Data on the enantioselectivity of hydrogenation of unsaturated precur-on the enantioselectivity of hydrogenation of unsaturated precursors of amino acids and unsaturated prochiral acids as well as on sors of amino acids and unsaturated prochiral acids as well as on the enantioselectivity of hydrosilylation of ketones are surveyed. the enantioselectivity of hydrosilylation of ketones are surveyed. The bibliography includes 77 references The bibliography includes 77 references. .

show abstract

Section: Organophosphorus Ligands Based On Hydroxy Acids 1 Synthesis ...mentioning

confidence: 99%

Section: Organophosphorus Ligands Based On Amino Acids 1 Synthesis Of...mentioning

confidence: 99%

Section: Use In Asymmetric Synthesismentioning

confidence: 99%

See 1 more Smart Citation

Natural compounds in the synthesis of chiral organophosphorous ligands

Толстиков¹,

Khlebnikova²,

Tolstikova³

et al. 2003

Russ. Chem. Rev.

View full text Add to dashboard Cite

show abstract

“…Both enantiomers of 2-methylsuccinamic acid 171 are important building blocks for the synthesis of biologically active compounds . The asymmetric hydrogenation of 2-methylenesuccinamic acid 170 would provide direct access to both enantiomers starting from itaconic acid anhydride .…”

Section: 9 Asymmetric Hydrogenation Of 2-methylenesuccinamic Acidmentioning

confidence: 99%

High-Throughput and Parallel Screening Methods in Asymmetric Hydrogenation

Jäkel¹,

Paciello²

2006

Chem. Rev.

223

View full text Add to dashboard Cite

“…3,4 Such an approach has been previously reported, albeit with moderate enantioselectivities, high catalyst loadings, and long reaction times (75-77% ee with a molar substrate-to-catalyst ratio (S/C) of 100 to 1000 over 20 h). 5 Herein we report a study performed to identify a more efficient asymmetric hydro-genation catalyst for the preparation of 2 together with initial investigations into process optimisation.…”

Section: Introductionmentioning

confidence: 99%

Highly Efficient Asymmetric Hydrogenation of 2-Methylenesuccinamic Acid Using a Rh-DuPHOS Catalyst

Cobley¹,

Lennon²,

Praquin³

et al. 2003

Org. Process Res. Dev.

View full text Add to dashboard Cite

An extremely efficient route to highly enantiomerically enriched 2-methylsuccinamic acid via asymmetric hydrogenation has been developed. By using [(S,S)-Et-DuPHOS Rh COD]BF 4 as the precatalyst under a set of broadly optimised process parameters, (R)-2-methylsuccinamic acid was obtained in 96% ee at a substrate-to-catalyst ratio (S/C) of 100000 (average turnover frequency ∼13000 h -1 ). The exclusion of chloridecontaining contaminants in the substrate was found to be crucial in obtaining exceptionally low catalyst loadings. This material could be upgraded with a single-crystal digestion to yield (R)-2-methylsuccinamic acid in >99.5% ee containing less than 1 ppm rhodium.

show abstract

Asymmetric Reactions Catalyzed by Chiral Metal Complexes. XLV. Efficient Preparation of Optically Active (S)-(-)-3-Methyl-.GAMMA.-butyrolactone by Catalytic Asymmetric Hydrogenation Using Chiral N-Substituted Pyrrolidinebisphosphine Rhodium Complexes.

Cited by 11 publications

References 0 publications

Natural compounds in the synthesis of chiral organophosphorous ligands

Natural compounds in the synthesis of chiral organophosphorous ligands

High-Throughput and Parallel Screening Methods in Asymmetric Hydrogenation

Highly Efficient Asymmetric Hydrogenation of 2-Methylenesuccinamic Acid Using a Rh-DuPHOS Catalyst

Contact Info

Product

Resources

About