FWF - Sila-Aldol - Aldol Reaction of the Heavier Carbon Homologues

Project: Research project

Description

The classical aldol reaction, particularly its role in the reversible formation and cleavage of carbon-carbon bonds, is one of the most important biosynthetic tools for life on Earth. The versatility and selectivity associated with this process are among the most extensively studied of all synthetic methods. For other group 14 elements, however, such bond-forming reactions were unknown until our group discovered the first aldol reaction of heavier carbon homologues (HCH aldol reaction) identified in cyclic silanes. From a synthetic standpoint, extension of the aldol reaction to acylsilanes, acylgermanes, and acylstannanes initiates a fundamental and direct approach towards carbon-group 14 metal based compounds, and complements standard techniques such as Wurtz reaction, hydrometalation, and transition-metal-catalyzed coupling reactions. Beyond its utility of creating β-hydroxy acyl subunits, the HCH aldol reaction can selectively deliver complex, unnatural frameworks with high non-carbon content that are challenging to access via other methods.
We aspire to explore the HCH aldol reaction, in continuation of our successful work with acylsilanes, as an orthogonal transformation and its applicability on a variety of systems by addressing the following:
- Synthesis of previously unknown group 14 bisacyl compounds as well as unknown group 14 enolates and bisenolates, which serve as precursor molecules for the HCH aldol reaction, including full spectroscopic and structural characterization of the isolated compounds.
- Exploration of intramolecular and intermolecular versions to achieve a comprehensive understanding of the unique and critical steps in the HCH aldol reaction.
- Computational studies to identify and support various inquires of the HCH aldol reaction:
- Locate potential reaction intermediates and calculate activation energies.
- Evaluate stereoselectivities.
- Determine physical properties of isolated products.
- Investigation of isolated group 14 bisacyl compounds with respect to their potential application as high performance photoinitiators.
StatusActive
Effective start/end date1/07/1930/06/22