New insight into the mechanism of catalytic hydrogenation allows the structure of the key intermediate in asymmetric hydrogenation to be predicted
โ Scribed by Jinquan Yu; Jonathan B. Spencer
- Publisher
- Elsevier Science
- Year
- 1998
- Tongue
- French
- Weight
- 616 KB
- Volume
- 54
- Category
- Article
- ISSN
- 0040-4020
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โฆ Synopsis
An approach has been developed to determine the regioselectivity of hydrometalation in homogeneous and heterogeneous hydrogenation of alkenes. By studying the electronic effects on the orientation of hydrometalation it is found with palladium and rhodium that this key step is a two electron process that can occur by two modes (a Pd 8+-H 8-or b Pd ~'-Hf~+). This provides valuable information about the structure of the metal-alkyl intermediate and helps rationalise how chiral induction occurs.
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## Abstract The scope of the novel chiral ligand ADA is evaluated in the catalytic asymmetric addition of ZnEt~2~ to ketones.
The 4-aryl-3,4-dihydrocoumarin 1 is a critical intermediate in the synthesis of two endothelin receptor antagonists. Asymmetry is introduced by the chiral catalytic hydrogenation of 2. Reduction occurs only if the lactone is open (3). A number of chiral ruthenium and rhodium organometallic species a