Hygroscopic Tunable Multishape Memory Effect in Cellulosic Macromolecular Networks with a Supramolecular Mesophase.

Tunable multishape memory polymers offer intriguing opportunities for memorizing multiple temporary shapes with tunable transition temperatures from one material composition. However, such multishape memory effects have been exclusively correlated with the thermomechanical behaviors of polymers, significantly limiting their applications in heat-sensitive scenarios. Here we report a nonthermal tunable multishape memory effect in covalently cross-linked cellulosic macromolecular networks, which spontaneously organize into supramolecular mesophases by water evaporation induced self-assembly. The supramolecular mesophase endows the network with a broad, reversible hygromechanical response combined with a unique moisture memory effect at ambient temperature, enabling diverse multishape memory behaviors (dual-, triple-, and quadruple-shape memory) under highly tunable and independent control of relative humidity (RH) alone. Significantly, such a hygroscopic tunable multishape memory effect readily extends the implications of shape memory polymers beyond the conventional thermomechanical regimes with potential advantages for biomedical applications.

Synthesis of 1,3-Aminoalcohols and Spirocyclic Azetidines via Tandem Hydroxymethylation and Aminomethylation Reaction of ß-Keto Phosphonates with N-Nosyl-O-(2-bromoethyl)hydroxylamine.

An unprecedented tandem α-hydroxymethylation and α-aminomethylation reaction of aromatic cyclic ß-keto phosphonates with N-nosyl-O-(2-bromoethyl)hydroxylamine in the presence of DBU base has been developed, affording a range of 1,3-aminoalcohols in good yields. The resultant products could be flexibly transformed into the spirocyclic and bispirocyclic azetidines via one step of Mitsunobu reaction. Mechanistic study revealed that hydroxylamine in situ generated the formaldehyde and nosylamide, which in turn triggered the sequential Horner-Wadsworth-Emmons, Michael, and aldol reactions.

Ring-Strain-Enabled Catalytic Asymmetric Umpolung C-O Bond-Forming Reactions of 1,2-Oxazetidines for the Synthesis of Functionalized Chiral Ethers.

An unprecedented catalytic asymmetric umpolung C-O bond-forming reaction of N-nosyl 1,2-oxazetidines with ß-keto esters has been achieved in the presence of a chiral phase-transfer catalyst, allowing access to a range of highly functionalized chiral ethers bearing quaternary and no adjacent stereogenic centers with high yields, excellent enantioselectivities, and diastereoselectivities (up to 97% ee and 20:1 dr). These versatile products could be flexibly transformed into biologically important chiral fused and spiro morpholines in two steps.