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• 66086-33-7 Di-tert-butyl acetylenedicarboxylate 
• 13831-03-3 tert-butyl prop-2-ynoate 
• 4422-95-1 1,3,5-benzene tris(carbonyl chloride) 
• 1907-33-1 lithium tert-butoxide 
• 75-65-0 tert-butyl alcohol 

Relevant academic research and scientific papers

A fast and convenient synthesis of new water-soluble, polyanionic dendrimers

Reasonably simple, efficient, and possessing aspects of generality, the methodology for the synthesis of new, water-soluble, dendrimeric polyesters with great potential applications as antiviral drugs in their own right is described. The essential aspect of the presented approach is a quite unique, immediate access to the polyanionic material at each generation during divergent synthesis. Six target polyanionic dendrimers (generations 1, 2, and 3) have been synthesized. The key monomers applied in this project were 1,3,5-benzenetricarboxylic acid derivatives, which also worked as direct precursors of the charged dendrimer surface.

Atomically Precise Crystalline Materials Based on Kinetically Inert Metal Ions via Reticular Mechanopolymerization

Atomistic control of the coordination environment of lattice ions and the distribution of metal sites within crystalline mixed-metal coordination polymers remain significant synthetic challenges. Herein is reported the mechanochemical synthesis of a reticular family of crystalline heterobimetallic metal–organic frameworks (MOFs) is now achieved by polymerization of molecular Ru2[II,III] complexes, featuring unprotected carboxylic acid substituents, with Cu(OAc)2. The resulting crystalline heterobimetallic MOFs are solid solutions of Ru2 and Cu2 sites housed within [M3L2] phases. The developed mechanochemical strategy is modular and allows for systematic control of the primary coordination sphere of the Ru2 sites within an isoreticular family of materials. This strategy is anticipated to provide a rational approach to atomically precise mixed-metal materials.

Cyclotrimerization of phenylacetylene catalyzed by a cobalt half-sandwich complex embedded in an engineered variant of transmembrane protein FhuA

An (η5-cyclopentadienyl)cobalt(i) complex was covalently incorporated into an engineered variant of the transmembrane protein ferric hydroxamate uptake protein component: A, FhuA ΔCVFtev, using a thiol-ene reaction. A CD spectrum shows the structural integrity of the biohybrid catalyst. MALDI-TOF of the segment containing the anchoring site for the cobalt complex Cys545 confirmed successful conjugation. This biohybrid catalyst catalyzed the cyclotrimerization of phenylacetylene to give a mixture of regioisomeric 1,2,4- and 1,3,5-triphenylbenzene in aqueous medium.

Divergent reactivity of a new dinuclear xanthene-bridged bis(iminopyridine) di-nickel complex with alkynes

The reaction of a dinucleating bis(iminopyridine) ligand L bearing a xanthene linker (L = N,N′-(2,7-di-tert-butyl-9,9-dimethyl-9H-xanthene-4,5-diyl)bis(1-(pyridin-2-yl)methanimine)) with Ni2(COD)2(DPA) (COD = cyclooctadiene, DPA = diphenylacetylene) leads to the formation of a new dinuclear complex Ni2(L)(DPA). Ni2(L)(DPA) can also be obtained in a one-pot reaction involving Ni(COD)2, DPA and L. The X-ray structure of Ni2(L)(DPA) reveals two square-planar Ni centers bridged by a DPA ligand. DFT calculations suggest that this species features NiI centers antiferromagnetically coupled to each other and their iminopyridine ligand radicals. Treatment of Ni2(L)(DPA) with one equivalent of ethyl propiolate (HCCCO2Et) forms the Ni2(L)(HCCCO2Et) complex. Addition of the second equivalent of ethyl propiolate leads to the observation of cyclotrimerised products by 1H NMR spectroscopy. Carrying out the reaction under catalytic conditions (1 mol% of Ni2(L)(DPA), 24 h, room temperature) transforms 89% of the substrate, forming primarily benzene products (triethyl benzene-1,2,4-tricarboxylate and triethyl benzene-1,3,5-tricarboxylate) in 68% yield, in a ca. 5:1 relative ratio. Increasing catalyst loading to 5 mol% leads to the full conversion of ethyl propiolate to benzene products; no cyclotetramerisation products were observed. In contrast, the reaction is significantly more sluggish with methyl propargyl ether. Using 1 mol% of the catalyst, only 25% conversion of methyl propargyl ether was observed within 24 h at room temperature. Furthermore, methyl propargyl ether demonstrates the formation of cyclooctatetraenes in significant amounts at a low catalyst concentration, whereas a higher catalyst concentration (5 mol%) leads to benzene products exclusively. Density functional theory was used to provide insight into the reaction mechanism, including structures of putative dinuclear metallocyclopentadiene and metallocycloheptatriene intermediates.

Efficient intermolecular [2 + 2 + 2] alkyne cyclotrimerization in aqueous medium using a ruthenium(IV) precatalyst

The dimeric bis(allyl)-ruthenium(IV) complex [{Ru(η3:η3-C10H16)(μ-Cl)Cl}2] (C10H16 = 2,7-dimethylocta-2,6-diene-1,8-diyl) was found to catalyze efficiently the [2 + 2 + 2] cyclization of terminal and internal alkynes in aqueous medium. Copyright

Diazadienes as Controlling Ligands in Homogeneous Catalysis, IX. Catalytic Cyclotetramerization of Propynoic Esters

Propynoic esters HCC-CO2R 2 react at low temperature in cyclohexane in the presence of precatalysts of the type diazadiene-nickel(0) complexes 3 and 4 or diazadiene-nickel-(η2-alkyne) complexes such as 5b to give exclusively or preponderantly c