A series of α-quaternary arylglycines were prepared in high optical purity (up to 98% ee) by α-alkylation of deprotonated α-aminonitriles derived by the Strecker reaction from (4S,5S)-5-amino-2,2-dimethyl-4-phenyl-1,3-dioxane. The procedure includes only chromatographic purification of the final products and is devoid of chromatography or crystallization operations on intermediates to raise the optical purity.

(1-Adamantyl)methyl glycidyl ether (AdaGE) is introduced as a versatile monomer for oxyanionic polymerization, enabling controlled incorporation of adamantyl moieties in aliphatic polyethers. Via copolymerization with ethoxyethyl glycidyl ether (EEGE) and subsequent cleavage of the acetal protection groups of EEGE, hydrophilic linear polyglycerols with an adjustable amount of pendant adamantyl moieties are obtained. The adamantyl unit permits control over thermal properties and solubility profile of these polymers (LCST). Additionally, AdaGE is utilized as a termination agent in carbanionic polymerization, affording adamantyl-terminated polymers. Using these structures as macroinitiators for the polymerization of ethylene oxide affords amphiphilic, in-chain adamantyl-functionalized block copolymers.

Enantioselective Synthesis of -Quaternary Amino Acids by Alkylation of Deprotonated -Aminonitriles. -An -alkylation of deprotonated -amino nitriles, prepared from chiral phenyldioxanamine (I) by Strecker reaction, leads to -quaternary arylglycines with high optical purity after hydrolysis and oxidative cleavage of the chiral auxiliary. The procedure requires only chromatographic purification of the final products. -(NETZ, I.; KUCUKDISLI, M.; OPATZ*, T.; J. Org. Chem. 80 (2015) 13, 6864-6869, http://dx.doi.org/10.1021/acs.joc.5b00868 ; Inst. Org. Chem., Johannes-Gutenberg-Univ., D-55128 Mainz, Germany; Eng.) -T. Stabingis 45-092