Hydrogen Transfer Reactions: Reductions and Beyond by Gabriela Guillena, Diego J. Ramón

By Gabriela Guillena, Diego J. Ramón

The sequence issues in present Chemistry Collections provides serious experiences from the magazine issues in present Chemistry equipped in topical volumes. The scope of assurance is all parts of chemical technological know-how together with the interfaces with similar disciplines equivalent to biology, drugs and fabrics technological know-how. The objective of every thematic quantity is to provide the non-specialist reader, no matter if in academia or undefined, a complete perception into a space the place new learn is rising that is of curiosity to a bigger medical audience.
each one assessment in the quantity severely surveys one point of that subject and areas it in the context of the amount as a complete. the main major advancements of the final five to ten years are awarded utilizing chosen examples to demonstrate the foundations mentioned. The assurance isn't really meant to be an exhaustive precis of the sphere or comprise huge amounts of information, yet should still otherwise be conceptual, targeting the methodological pondering that might let the non-specialist reader to appreciate the data awarded. Contributions additionally supply an outlook on power destiny advancements within the field.

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016 mol% relative to the substrate) [143]. In order to study the electronic and steric effects of the trans-CO/Br PNNP type of iron(II) complexes the orto- and para-substituted phenyl groups were introduced into the phosphorus donors (examples 162b–166b) while the (S,S)-1,2-diphenylethylenediamine moiety was retained. Among them, only 162b and 164b were active catalysts in the ATH experiments reducing acetophenone to the corresponding alcohol; 164b had too much steric crowding around the iron centre, while 165b and 166b were too electron-poor and were inactive in ATH.

While the reduction of acetophenone in the presence of the complex [Ru(II)–93] and applying S/C/ NaOH 100:1:5 was sluggish at room temperature, it was enormously accelerated in refluxing propan-2-ol, thus reaching nearly quantitative conversion and a 95 % ee in 20 min. Although, in general, phosphinite-ferrocene-based ligands did not overpass the efficiency of the above-mentioned phosphine-ferrocene ligands in the ruthenium ATH catalysis, they offer a great opportunity for further investigation due to their outstanding air stability and ease of preparation.

The homogeneous cationic complex 134 was entrapped within mesoporous silica Me-SBA-15 or MeSBA-16 and used in ultra-sound-promoted ATH of various aromatic ketones (ringsubstituted acetophenones and acetylnaphthalenes) in water with HCO2Na (Fig. 37). In comparison to the neutral Cp*Rh-TSDPEN version (as depicted in Fig. 36), the cationic version showed higher initial activity while ultra-sound irradiation could significantly enhance the reaction rate. They also showed that the catalyst with the chiral Rh functionality entrapped within Me-SBA-16 could be reused nine times without significantly affecting the enantioselectivity.

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