Development of new reactions catalyzed by copper(I) complexes using silylboranes and bisboronates as pronucleophiles
(2014)
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- Authors
- Supervisors
- Riant, Olivier
- Abstract
- The development of new catalytic methods has been an area of intense research in recent years and particular efforts are currently devoted to transition-metal-catalyzed reactions. We are thus interested in developing new reactions catalyzed by copper(I) complexes. In the chapter 1, the objective was the extension of 1,4-addition/aldolisation reactions developed earlier in our group. Concerning the silylation reaction, we were able to isolate several interesting adducts with moderate to good yields but with low diastereoselectivities in almost all cases. About the borylation reaction, two strategies for the synthesis of new cationic copper(I) complexes bearing a bifluoride counteranion were described. These complexes were therefore used in our reaction and have shown a good reactivity. However, the selectivities were low in most cases. In the chapter 2, our interest lies in the addition of silicon nucleophile to acid derivatives, thus generating acylsilanes. They are versatile intermediates in organic synthesis and are used mainly as umpolung reagents for the preparation of carbonyl derivatives. An efficient method to synthesize these compounds, starting from easy-to-form anhydrides, was described here with good to excellent yields. In the chapter 3, the first example of enantioselective addition of a silicon nucleophile to aldehydes catalyzed by our newly developed copper(I) complexes are reported. A series of aromatic and aliphatic aldehydes were converted to the corresponding α-hydroxysilanes in excellent ee and very good yields.
- Affiliations
Citations
Cirriez, V. (2014). Development of new reactions catalyzed by copper(I) complexes using silylboranes and bisboronates as pronucleophiles. https://hdl.handle.net/2078.5/55378