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Published on: August 1, 2018
Cyclic esters and cyclodepsipeptides derived from lactide and 2,5-morpholinediones
Malcolm H Chisholm1, Judith C Gallucci, Hongfeng Yin
1Department of Chemistry, Ohio State University, 100 West 18th Avenue, Columbus, OH 43210-1185, USA. chisholm@chemistry.ohio-state.edu
Summary
A novel lithiated polystyrene support facilitates ring-opening of cyclic esters, enabling chemical amplification and high yields of specific cyclic ester rings. This dynamic combinatorial chemistry approach offers efficient synthesis of complex macrocycles.
Area of Science:
- Polymer Chemistry
- Organic Synthesis
- Supramolecular Chemistry
Background:
- Functionalized solid supports are crucial for developing novel catalytic systems.
- Ring-opening of cyclic esters is a key reaction in polymer synthesis and macrocycle formation.
- Dynamic combinatorial chemistry offers powerful strategies for molecular assembly and amplification.
Purpose of the Study:
- To investigate the ring-opening activity of a lithiated polystyrene support with cyclic esters.
- To explore the potential for chemical amplification and macrocycle synthesis using this system.
- To characterize the products formed, including novel cyclic ester rings.
Main Methods:
- Reaction of n-butyllithium with a functionalized polystyrene support to create a lithiated species.
- Ring-opening of L-lactide, rac-lactide, and 2,5-morpholinediones with the lithiated support.
- Characterization of released cyclic esters using electrospray ionization mass spectrometry (ESI-MS) and gel-permeation chromatography (GPC).
- Selective precipitation of macrocycles using sodium tetraphenylborate (NaBPh4).
- Single-crystal X-ray diffraction studies of specific macrocycles and their complexes.
Main Results:
- The lithiated polystyrene support PS-C6H4CH2NHLi(LiBu)x is active in the ring-opening of cyclic esters.
- Reversible release of cyclic esters from the support was observed upon heating.
- Chemical amplification of lactide was achieved, leading to the formation of an 18-membered ring ((MeCHC(O)O)6) in >80% yield.
- Novel 18- and 24-membered cyclic ester rings were synthesized and characterized, including their X-ray crystal structures.
- Metallated supports derived from Me2Mg and Et2Zn showed lower reactivity but some ring-enlarging ability.
Conclusions:
- The lithiated polystyrene support serves as an effective platform for dynamic ring-opening and macrocycle synthesis.
- The system demonstrates a successful application of chemical amplification from a dynamic combinatorial library for lactide.
- This approach provides a versatile route to synthesize well-defined cyclic ester macrocycles with potential applications in materials science and medicinal chemistry.
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