N,N-Diisopropylferrocenecarboxamide can be enantioselectively deprotometalated by combining butyllithium with (−)-sparteine in diethyl ether at low temperature. It is of interest to identify conditions that could allow substrates bearing more reactive functional groups (such as esters and ketones) to be similarly converted. We here report our efforts to use different chiral lithium–zinc bases, made from a simple chiral lithium amide, (R,R)- or (S,S)-lithium bis(1-phenylethyl)amide (PEALi), for the enantioselective deprotonation of N,N-diisopropylferrocenecarboxamide. First, different zinc-based in situ traps were employed to intercept the formed ferrocenyllithium; optimization using enantiopure lithium bis[1-(S)-phenylethyl]amide ((S)-PEALi) led to the 2-iodo derivative in 96% yield and 69% ee in favor of the R_P enantiomer. The method was extended to N,N-dimethylferrocenecarboxamide, morpholinoferrocenecarboxamide and N,N-diethylferrocenecarboxamide; for the latter, similar yield and enantioselectivity were recorded. DFT calculations on a model reaction showed very small differences between the activation energies leading to (R_P)- and (S_P)-2-lithioferrocenecarboxamides. Next, the behavior of various mixed amino-alkyl lithium zincates of the types R₂[(S)-PEA]ZnLi and R₂[(S)-PEA]₂ZnLi₂ (R = alkyl) was studied, notably by varying the reaction temperature and time, and the amount of base. The best results were obtained with Me₂[(S)-PEA]₂ZnLi₂, affording the 2-iodo derivative in 97% yield and 86% ee in favor of the S_P enantiomer.

The utilization of dodecaborate boron clusters, [B₁₂X₁₂]²⁻ (X = Cl, Br, or I), as membrane carriers has been demonstrated recently, and their activity is known to be due to their superchaotropic nature. In this work, the mono-alkylation of [B₁₂Br₁₁OH]²⁻ to functionalize it with an aliphatic spacer was developed with a view to expanding the known chemical space of membrane carriers based on [B₁₂Br₁₂]²⁻. A new and improved facile route for the preparation of [B₁₂Br₁₁OH]²⁻, which is an important precursor to other [B₁₂Br₁₁OR]²⁻ species, is reported. Various alkoxylated [B₁₂Br₁₁O(CH₂)₅Z]²⁻ (Z = OH, N(CO)₂C₆H₄, CN and N₃) derivatives were prepared via a divergent synthesis based on [B₁₂Br₁₁O(CH₂)₅Br]²⁻. One of the newly synthesized compounds was utilized as a membrane carrier, and its impact on cell viability was examined.

Having access to safe drinking water is one of the 17 sustainable development goals defined by the United Nations (UN). However, many settlements around the globe have limited access to drinkable water due to non-anthropogenic pollution of the water sources. One of those pollutants is fluoride, which can induce major health problems. In this manuscript, we report on a post synthetic functionalization of metal organic frameworks for the sensing of fluoride in water. The proposed thermal condensation methodology allows for a high yield of functionalization using few steps, reducing reagent costs and generating minimal by-products. We identified a Rhodamine B functionalized Al-BDC-NH${}_2$ metal organic framework as one particularly suitable for fluoride detection in water.