Exploitation of Mechanistic Product Selectivity for the Two‐step Synthesis of Optically Active Bio‐derived Cyclic Carbonates Incorporating Amino Acids

CABRERA, Diego Jaraba, ÁLVAREZ-MIGUEL, Lucía, RODRÍGUEZ, Adrián Hernando, HAMILTON, Alexander, MOSQUERA, Marta EG and WHITEOAK, Christopher J (2024). Exploitation of Mechanistic Product Selectivity for the Two‐step Synthesis of Optically Active Bio‐derived Cyclic Carbonates Incorporating Amino Acids. European Journal of Organic Chemistry: e202400219.

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Abstract

The synthesis of bio‐derived cyclic carbonates is attracting a lot of attention as the incorporation of bio‐derived functionality into these compounds provides the opportunity to prepare previously unknown structures, whilst also improving their sustainability profiles. This study presents a facile preparation of diastereomerically pure bio‐derived cyclic carbonates displaying a range of optical rotation values. These compounds are obtained from glycidol, amino acids and CO2 in a facile two‐step approach. Initially, the diastereomerically pure amino acid functionalised epoxides are prepared through a robust Steglich esterification of enantiopure glycidol (R or S) and an amino acid (D or L). Thereafter, in a second step, cycloaddition of the epoxide with CO2 results in the retention of the initial stereochemistry of the epoxide, furnishing novel diastereomerically pure and optically active cyclic carbonate products. A DFT study has explained the basis of this observed retention of configuration for these compounds. Further, results from this DFT study also provide new mechanistic information concerning a co‐catalyst‐free cycloaddition reaction starting from glycidol when using the gallium‐catalyst, which is found to operate through metal‐ligand cooperativity.

Item Type:	Article
Uncontrolled Keywords:	0304 Medicinal and Biomolecular Chemistry; 0305 Organic Chemistry; Organic Chemistry; 3404 Medicinal and biomolecular chemistry; 3405 Organic chemistry
Identification Number:	https://doi.org/10.1002/ejoc.202400219
SWORD Depositor:	Symplectic Elements
Depositing User:	Symplectic Elements
Date Deposited:	07 Mar 2024 12:45
Last Modified:	26 Mar 2024 12:30
URI:	https://shura.shu.ac.uk/id/eprint/33364

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