Highly convergent synthesis of C3- or C2-symmetric carbohydrate macrocycles.

[structure: see text] A highly convergent strategy for the synthesis of C3- or C2-symmetric oligosaccharide macrocycles is reported. Molecular modeling indicates these macrocycles possess sterically congested cavities. Weak host-guest interactions are observed that should be beneficial for applications such as functionalized molecular pores.

Regioselective [2 + 2 + 2] cycloaddition of a nickel-benzyne complex with 1,3-diynes.

[reaction: see text] Reactions of nickel(0)-benzyne complexes with a range of symmetrically substituted 1,3-diynes in the presence of triethylphosphine lead to the regioselective formation of 2,3-dialkynyl naphthalenes. The regioselectivity can be reversed when the diyne possesses substituents of high steric bulk, allowing selective formation of either symmetric dialkynyl naphthalene.

Synthesis and photocleavage of a new dimeric bis(o-nitrobenzyl) diether tether.

A new photocleavable linker, 4,4'-bis(alkoxymethyl-3,3'-dinitro)biphenyl, is reported that undergoes photolysis at two positions to release two equivalents of primary, secondary, or benzylic alcohol in yields that are higher than those obtained from the analogous monomeric o-nitrobenzyl ethers.

A light-gated synthetic ion channel.

A gated synthetic ion channel with beta-cyclodextrin as the pore and azobenzene as the gate is reported. Irradiation converts a tethered trans-azobenzene to cis-azobenzene which likely transforms the channel from a self-inclusion complex to a dissociated structure. This transformation results in an increase in anion transport and a decrease in cation transport across a phospholipid vesicle membrane.

Increasing pH causes faster anion-and cation-transport rates through a synthetic ion channel.

Ion-channel mimics are able to transmit electrical signals across phospholipid membranes, and can be envisioned as nanoswitches for molecular electronics. Here, we reported the use of pH to alter ion-transport rates through a synthetic aminocyclodextrin ion channel. Both cation- and anion-transport rates were found to increase with an increase in pH due to the unique electrostatics of the multiple ammonium groups that line the channel pore. Such pH regulation of ion transport rates is unique and can be exploited for sensing applications.

Preparation of discrete oligoethers: synthesis of pentabutylene glycol and hexapropylene glycol by two complementary methods.

Two experimentally facile methods for the preparation of discrete oligoethers are reported. The first involves an iterative sequence of oxidation, acetal formation, and reductive ring opening for the synthesis of penta-1,4-butylene glycol. The second method is also iterative, comprising phase-transfer etherification and end-group deprotection to form hexa-1,3-propylene glycol. These methods offer significantly improved yields and purification protocols over previously reported syntheses.

Synthesis of readily modifiable cyclodextrin analogues via cyclodimerization of an alkynyl-azido trisaccharide.

A convergent strategy for the synthesis of beta-cyclodextrin analogues is reported, utilizing preferential cyclodimerization of an azido-alkyne trisaccharide via Cu(I)-catalyzed [3 + 2] dipolar cycloaddition of the alkyne and azide functional groups. The resultant oligosaccharide macrocycle retains the binding propensity of cyclodextrins, as demonstrated by the similar ANS association constants measured for macrocycle 1 and beta-cyclodextrin. This new synthetic strategy opens up new avenues for modular preparation of functionally diverse cyclodextrin analogues that are otherwise inaccessible.