Publications by authors named "Alberto Steffani"
Article Synopsis
- The study explores a titanium(III)-catalyzed method for synthesizing α-hydroxyketones from ketones and nitriles, demonstrating an efficient and stereoselective process.
- A series of advanced techniques, including EPR, ESI-MS, and DFT calculations, were used to uncover the mechanism, highlighting that the formation of C-C bonds is the rate-limiting step controlled by radical combinations of titanium(III) species.
- The research identifies a key cationic titanocene-nitrile complex and explains how the addition of Et3N·HCl enhances yield and enantioselectivity by facilitating the radical coupling process.
Previously we reported the redox-neutral atom economic rhodium catalyzed coupling of terminal alkynes with carboxylic acids using the DPEphos ligand. We herein present a thorough mechanistic investigation applying various spectroscopic and spectrometric methods (NMR, in situ-IR, ESI-MS) in combination with DFT calculations. Our findings show that in contrast to the originally proposed mechanism, the catalytic cycle involves an intramolecular protonation and not an oxidative insertion of rhodium in the OH bond of the carboxylic acid.
View Article and Find Full Text PDF[P9]+ [Al(OR(F))4)]-, the salt of a homopolyatomic phosphorus cation.
Angew Chem Int Ed Engl
June 2012
Positive at last: The first condensed-phase homopolyatomic phosphorus cation [P(9)](+) was prepared using a combination of the oxidant [NO](+) and weakly coordinating anion, [Al{OC(CF(3))(3)}(4)](-). [P(9)](+) consists of two P(5) cages linked by a phosphonium atom to give a D(2d)-symmetric Zintl cluster. NMR (see picture), Raman, and IR spectroscopy, mass spectrometry, and quantum-chemical calculations confirmed the structure.
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