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Abstract Several charge‐containing TADDOL salts were synthesized and used as organocatalysts in asymmetric Diels–Alder and hetero‐Diels–Alder reactions. Their catalytic activity was found to exceed that of a noncharged analog while maintaining or improving upon the enantioselectivity. The enhanced activities of the TADDOL salts enabled them to act as presumed hydrogen bond donor catalysts in the Diels–Alder and hetero‐Diels–Alder reactions of 1,3‐cyclohexadiene with methyl vinyl ketone at 40°C and 2‐phenoxy‐1,3‐butadiene with ethyl glyoxylate at room temperature, respectively. Given the ionic nature of these charge‐activated catalysts, it also proved possible to recycle and reuse the TADDOL without chromatography or the need for a recrystallization.
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Amine-Catalyzed Chain Polymerization of Ethyl Glyoxylate from Alcohol and Thiol Initiators
Polyacetals have significant potential as degradable polymers, but aldehyde polymerizations are generally difficult to control. Here we show that polymerization of ethyl glyoxylate can be initiated from alcohols or thiols by activation with triethylamine to afford poly(ethyl glyoxylate) with controllable molecular weights and relatively low dispersities (Đ = 1.3–1.4), as evidenced by MALDI-TOF mass spectrometry. Stabilization against depolymerization by chain-capping with benzyl chloroformate was found to proceed without side reactions observed from chain-capping with tolyl isocyanate. The use of the stronger base DBU leads to competing side reactions that limit polymer molecular weight.
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- Award ID(s):
- 1904932
- PAR ID:
- 10213768
- Date Published:
- Journal Name:
- ACS Macro Letters
- Volume:
- 10
- ISSN:
- 2161-1653
- Page Range / eLocation ID:
- 370 - 374
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1021/acsmacrolett.0c00865
