Disulfide Bonds as Functional Tethers in Metal-Organic Frameworks.

The functionality of metal-organic frameworks (MOFs) is often encoded by specific chemical moieties found within these architectures. As such, new techniques to install increasingly more complex functionalities in MOFs are regularly being reported in the literature. One such functional group is the disulfide bond.

Deinterpenetration of IRMOF-9.

One of the iconic characteristics of metal-organic frameworks (MOFs) is the possesssion of guest-accessible pores. Increasing pore size has a direct and often beneficial impact on a MOF's adsorption and separation properties. However, as pore size increases, the resulting void spaces are often filled by interpenetrated frameworks, where one or more networks crystallize within the pore system of another identical network, reducing the MOF's free volume and pore size.

Disulfide-Driven Pore Functionalization of Metal-Organic Frameworks.

Post-synthetic modification (PSM) imparts additional functionality to metal-organic frameworks (MOFs) that is often difficult to access using solvothermal synthesis. As such, expanding the repertory of PSM reactions available to the practitioner is of increased importance for the generation of materials tailored for desired applications. Herein, a method is described for the protecting group-free installation of diverse functional groups within the pores of a MIL-53(Al) analogue via disulfide bond formation.

Mechanistic Investigation of the Synthesis of Dianionic In-Derived Coordination Polymers.

The mechanism of formation of crystalline coordination polymers is as complex as the architectures themselves. In this Communication, we detail a three-tiered approach using density functional theory (DFT) analysis, synthesis, and Raman spectroscopy to study the formation of coordination polymers. Specifically, the previously reported coordination polymers YCM-22 and YCM-51 containing the [In(COR)X] (X = halogen) molecular building unit (MBU) were investigated.

Anion-Cation Mediated Structural Rearrangement of an In-derived Three-Dimensional Interpenetrated Metal-Organic Framework.

Postsynthetic modification of metal-organic frameworks (MOFs) has proven an effective method of synthesizing architectures that have proven challenging to produce via classic solvothermal means. Herein we report the anion-cation assisted solid-state transformation of a three-dimensional MOF (ATF-1) to a series of two-dimensional structures (YCM-21-Z) via treatment with quaternary ammonium halides. It is important to note that this reaction requires no exogoneous building blocks (inorganic cation and/or organic linker) for conversion to occur.

An artemisinin-derived dimer has highly potent anti-cytomegalovirus (CMV) and anti-cancer activities.

We recently reported that two artemisinin-derived dimers (dimer primary alcohol 606 and dimer sulfone 4-carbamate 832-4) are significantly more potent in inhibiting human cytomegalovirus (CMV) replication than artemisinin-derived monomers. In our continued evaluation of the activities of artemisinins in CMV inhibition, twelve artemisinin-derived dimers and five artemisinin-derived monomers were used. Dimers as a group were found to be potent inhibitors of CMV replication.

Cyanocuprates convert carboxylic acids directly into ketones.

Carboxylic acids were converted directly in 56-99% yields into methyl, n-butyl, and isopropyl ketones using excess cyanocuprates R(2)CuLi·LiCN. A substrate with a stereocenter α to the carboxylic acid was converted into ketones with very little loss of enantiomeric purity. A variety of functional groups were tolerated including aryl bromides.

Highly stereocontrolled and regiocontrolled syntheses of 2,3,4-trisubstituted alkanoates and lactones.

New chlorodiols (±)-3 and (±)-5 are densely functionalized and versatile synthons. They are converted in one step on a gram scale into 2-chlorolactones (±)-6 and (±)-7 and into 4-hydroxy glycidate esters (±)-9 and (±)-10. The 4-hydroxy glycidate esters (±)-9 and (±)-10 are converted stereospecifically and regiospecifically into oxazolines (±)-13 and (±)-14 and into cyclic carbamates (±)-18-(±)-20.

α-Chloro-β,γ-ethylenic esters: enantiocontrolled synthesis and substitutions.

Chiral nonracemic γ-seleno-α,β-ethylenic esters, when treated with sulfuryl chloride and ethyl vinyl ether in hexanes, produced α-chloro-β,γ-ethylenic esters in 65-75% yields, with ee values of 95-97%, and with 1,3-syn transfer of chirality. Reaction of these allylic chloride electrophiles with methylcuprate and with sodium azide nucleophiles afforded exclusively γ-substituted-α,β-ethylenic esters with faithful anti-transfer of chirality on multigram scale.