Hydrothermal Synthesis and Structure of a New 3D Lanthanide—Carboxylate Framework,[La（btec）1／2（H2btec）1／2（H2O）]n（H4btec=1,2,4,5—Benzeneteracarboxylic acid）

The title complex, [La(btec)_1/2(H₂btec)_1/2 (H₂O)]_n (H₄btec= 1, 2,4,5‐benzenetetracarboxylic acid) (1) was synthesized by the hydrothermal reaction of 1,2,4,5‐benzenetetracarboxylic dianhydride with La(NO₃)₃·6H₂O in H₂O, and crystallizes in the triclinic system, space group P‐1 with a = 0.64403(3) nm, b = 0.94500(4) nm, c = 0.96380(5) nm, a = 88.535(2)°, β = 100.314(2)°, γ = 76.6470(10)°, V = 1.60968(10) nm³, Z = 2, and final R = 0.0274, R_w = 0.0735. In 1, each La(m) ion is coordinated by eight oxygen atoms from six carboxylate groups and one coordinated water molecule. Two different coordination modes of H₄btec were present in the structure, one of which contains two protonated carboxylate groups to balance the charge.     

Synthesis,characterization, and star polymer assembly of boronic acid end‐functionalized polycaprolactone

Boronic acid end‐functionalized polycaprolactone (PCL) polymers were synthesized by ring‐opening polymerization using a pinacol boronate ester‐containing (Bpin) initiator. The polymerization provides access to boron‐terminated polymers (i.e. Bpin‐PCL‐OH) with narrow molecular weight distributions (PDI = 1.09). Postsynthetic manipulation of the polymer's terminal hydroxyl group by copper‐catalyzed azide‐alkyne cycloaddition chemistry provides a series of bis end‐functionalized polymers with significant structural diversity at the termini. Deprotection of the boronate ester end group was accomplished with an acidic solid phase DOWEX resin. The boronate ester deprotection methodology does not result in hydrolysis of the polymeric backbone. The boronic acid‐tipped polymers were converted into star polymer assemblies using thermal dehydration and ligand‐facilitated trimerization. Thermal dehydration of (HO)₂B‐PCL‐OAc to the corresponding boroxine‐based star polymer assembly was inefficient and lead to degradation products. Ligand‐facilitated trimerization using either pyridine or 7‐azaindole as the Lewis base was efficient and mild. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

A New Synthetic Route to 12-Oxo-1, 15-pentadecanlactam

12-Oxo-1,15-pentadecanlactam 7 was synthesized from cyclododecanone with a totalyield of 36% in a seven-step reaction. The azide 5 to 12-nitro-1,15-pentadecanlactam 6 is the key step featured by direct ring expansion.     

SAMPL6 challenge results from $$pK_a$$ predictions based on a general Gaussian process model

A variety of fields would benefit from accurate \(pK_a\) predictions, especially drug design due to the effect a change in ionization state can have on a molecule’s physiochemical properties. Participants in the recent SAMPL6 blind challenge were asked to submit predictions for microscopic and macroscopic \(pK_a\)s of 24 drug like small molecules. We recently built a general model for predicting \(pK_a\)s using a Gaussian process regression trained using physical and chemical features of each ionizable group. Our pipeline takes a molecular graph and uses the OpenEye Toolkits to calculate features describing the removal of a proton. These features are fed into a Scikit-learn Gaussian process to predict microscopic \(pK_a\)s which are then used to analytically determine macroscopic \(pK_a\)s. Our Gaussian process is trained on a set of 2700 macroscopic \(pK_a\)s from monoprotic and select diprotic molecules. Here, we share our results for microscopic and macroscopic predictions in the SAMPL6 challenge. Overall, we ranked in the middle of the pack compared to other participants, but our fairly good agreement with experiment is still promising considering the challenge molecules are chemically diverse and often polyprotic while our training set is predominately monoprotic. Of particular importance to us when building this model was to include an uncertainty estimate based on the chemistry of the molecule that would reflect the likely accuracy of our prediction. Our model reports large uncertainties for the molecules that appear to have chemistry outside our domain of applicability, along with good agreement in quantile–quantile plots, indicating it can predict its own accuracy. The challenge highlighted a variety of means to improve our model, including adding more polyprotic molecules to our training set and more carefully considering what functional groups we do or do not identify as ionizable.     

Palladium-catalyzed tandem cyclization/Suzuki coupling of 1,6-enynes: reaction scope and mechanism

A palldium(0)-catalyzed tandem cyclization/Suzuki coupling reaction of various 1,6-enyne substrates was developed. This Pd-catalyzed enyne cyclization reaction represents a new process for the synthesis of stereodefined alpha-arylmethylene-gamma-butyrolactones, lactams, multifunctional tetrahydrofurans, pyrrolidines, and cyclopentanes. The mechanism of the reaction was studied by the employment of different enyne isomers and boronic acids; a pi-allyl palladium intermediate was suggested to explain the formation of the cyclic products. The stereochemistry of this reaction can be well explained by a chairlike transition state.     

A Frustrated and Confused Lewis Pair

We report a new class of frustrated Lewis pairs (FLPs) by the hydroboration of bulky isocyanates ^iPr2ArNCO (^iPr2Ar=2,6‐iPr₂C₆H₃) and ^Ph2tBuArNCO (^Ph2tBuAr=2,6‐Ph₂‐4‐tBuC₆H₂) with Piers’ borane (HB(C₆F₅)₂). While hydroboration of smaller isocyanates such as ^iPr2ArNCO leads to isocyanate—N/B FLP adducts, hydroboration of the bulkier ^Ph2tBuArNCO allows isolation of the substrate‐free aminoborane with a short, covalent N?B bond. This confused FLP reversibly binds unsaturated substrates such as isocyanates and isocyanides, suggesting the intermediacy of a “normal” FLP along the reaction pathway, supported by high‐level DFT studies and variable‐temperature NMR spectroscopy. These results underscore the possibility of FLP behavior in systems that possess no obvious frustrated Lewis acid–base interaction.     

Synthesis,Structures, and Fluorescent Properties of Three Cobalt‐Based Coordination Polymers with a Rigid Tripodal Carboxylate Ligand

Three cobalt(II) coordination polymers, [Co₂(tatb)₂(2,2′‐bipy)₂ (H₂O)₂ · DMA · 2H₂O] ( 1 ), [Co₂(tatb)₂(1,10‐phen)₂(H₂O)₂ · 2H₂O] ( 2 ) and [Co(tatb)(1,3‐dpp) · H₂O] ( 3 ) (H₃tatb = 4,4′,4′′‐(1,3,5‐triazine‐2,4,6‐triyl)tribenzoic acid; 2,2′‐bipy = 2,2′‐bipyridyl; 1,10‐phen = 1,10‐phenanthroline; 1,3‐dpp = 1,3‐bis(pyridin‐4‐yl)propane), were synthesized solvothermally and characterized by single‐crystal and powder X‐ray diffraction (PXRD), as well as IR spectroscopy. Complexes 1 and 2 exhibit 1D double‐chain structures, which further connect into interesting 3D networks by hydrogen bond and strong π–π interactions. Complex 3 possesses 2D 4⁴‐sql topology, which is packed parallel in an AA fashion. Moreover, thermal stability properties and photoluminescence properties of 1 , 2 and 3 were also investigated.     

Making High Selective Molecule Imprinting Polymer (MIP) In Polar Solvent

IntroductionMoleculeimprintingtechnologyhasmadegreatprogressinmakingchiralstationaryphasewithpredeterminedchiralselectivityagainstenantiomerssuchasaminoacidandtheirderivatives;sugarandtheirderivatives;naproxenandmethylbenZylamine'-'.Functionalmonomer...