Study of Intermediates in Iridium–(Phosphoramidite,Olefin)-Catalyzed Enantioselective Allylic Substitution
| Autor: | Simon L. Rössler, Simon Krautwald, Erick M. Carreira |
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| Rok vydání: | 2017 |
| Předmět: |
Models
Molecular Allylic rearrangement Stereochemistry chemistry.chemical_element Alkenes Crystallography X-Ray Iridium 010402 general chemistry 01 natural sciences Biochemistry Catalysis Organophosphorus Compounds Colloid and Surface Chemistry Nucleophile Organometallic Compounds Olefin fiber Phosphoramidite Molecular Structure 010405 organic chemistry Chemistry organic chemicals Enantioselective synthesis food and beverages Stereoisomerism General Chemistry Nuclear magnetic resonance spectroscopy Combinatorial chemistry 0104 chemical sciences 3. Good health Allyl Compounds Kinetics |
| Zdroj: | Journal of the American Chemical Society |
| ISSN: | 1520-5126 0002-7863 |
| DOI: | 10.1021/jacs.6b12421 |
| Popis: | Experimental mechanistic studies of iridium-catalyzed, enantioselective allylic substitution enabled by (phosphoramidite,olefin) ligands are reported. (η2-Allylic alcohol)iridium(I) and (η3-allyl)iridium(III) complexes were synthesized and characterized by NMR spectroscopy as well as X-ray crystallography. The substrate complexes are catalytically and kinetically competent to be intermediates in allylic substitutions of branched, racemic allylic alcohols with various nucleophiles. In addition, we have identified an off-cycle pathway involving reversible binding of molecular oxygen to iridium, which contributes to the air tolerance of the catalyst system. |
| Databáze: | OpenAIRE |
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