- Mechanistic insight into the stereoselective cationic polymerization of vinyl ethers
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The control of the tacticity of synthetic polymers enables the realization of emergent physical properties from readily available starting materials. While stereodefined polymers derived from nonpolar vinyl monomers can be efficiently prepared using early transition metal catalysts, general methods for the stereoselective polymerization of polar vinyl monomers remain underdeveloped. We recently demonstrated asymmetric ion pairing catalysis as an effective approach to achieve stereoselective cationic polymerization of vinyl ethers. Herein, we provide a deeper understanding of stereoselective ion-pairing polymerization through comprehensive experimental and computational studies. These findings demonstrate the importance of ligand deceleration effects for the identification of reaction conditions that enhance stereoselectivity, which was supported by computational studies that identified the solution-state catalyst structure. An evaluation of monomer substrates with systematic variations in steric parameters and functional group identities established key structure-reactivity relationships for stereoselective homo- and copolymerization. Expansion of the monomer scope to include enantioenriched vinyl ethers enabled the preparation of an isotactic poly(vinyl ether) with the highest stereoselectivity (95.1% ± 0.1 meso diads) reported to date, which occurred when monomer and catalyst stereochemistry were fully matched under a triple diastereocontrol model. The more complete understanding of stereoselective cationic polymerization reported herein offers a foundation for the design of improved catalytic systems and for the translation of isotactic poly(vinyl ether)s to applied areas.
- Leibfarth, Frank A.,Varner, Travis P.,Teator, Aaron J.,Reddi, Yernaidu,Jacky, Paige E.,Cramer, Christopher J.
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- Calcium Carbide Looping System for Acetaldehyde Manufacturing from Virtually any Carbon Source
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A vinylation/devinylation looping system for acetaldehyde manufacturing was evaluated. Vinylation of iso-butanol with calcium carbide under solvent-free conditions was combined with hydrolysis of the resulting iso-butyl vinyl ether under slightly acidic conditions. Acetaldehyde produced by hydrolysis was collected from the reaction mixture by simple distillation, and the remaining alcohol was redirected to the vinylation step. All the inorganic co-reagents can be looped as well, and the full sequence is totally sustainable. A complete acetaldehyde manufacturing cycle was proposed on the basis of the developed procedure. The cycle was fed with calcium carbide and produced the aldehyde as a single product in a total preparative yield of 97 %. No solvents, hydrocarbons, or metal catalysts were needed to maintain the cycle. As calcium carbide in principle can be synthesized from virtually any source of carbon, the developed technology represents an excellent example of biomass and waste conversion into a valuable industrial product.
- Rodygin, Konstantin S.,Lotsman, Kristina A.,Ananikov, Valentine P.
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p. 3679 - 3685
(2020/06/17)
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- 3-(2-Acylamino-1-Hydroxyethyl)-Morpholine Derivatives and Their Use as Bace Inhibitors
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The present invention provides BACE inhibitors of Formula (I); methods for their use and preparation, and intermediates useful for their preparation.
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Page/Page column 23
(2008/06/13)
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