Negishi's Reagent Versus Rosenthal's Reagent in the Formation of Zirconacyclopentadienes

Zirconacyclopentadienes are versatile precursors for a large number of heteroles, which are accessible by Zr-element exchange reactions. The vast majority of reports describe their preparation by the use of Negishi′s reagent, which is a species that is formed in situ. The zirconacyclopentadiene is then formed by the addition of one equivalent of a diyne or two equivalents of a monoyne moiety to this Negishi species. Another route involves Rosenthal′s reagent (Cp₂Zr(py)Me₃SiC≡CSiMe₃), which then reacts with a diyne or monoyne moiety. In this work, the efficiency of both routes was compared in terms of reaction time, stability of the product in the reaction mixture, and yield. The synthetic implications of using both routes are evaluated. Novel zirconacyclopentadienes were synthesized, characterized directly from the reaction mixture, and crystal structures could be obtained in most cases.     

A Lax pair structure for the half-wave maps equation

We consider the half-wave maps equation

$$\begin{aligned} \partial _t \vec {S} = \vec {S} \wedge |\nabla | \vec {S}, \end{aligned}$$

where \(\vec {S}= \vec {S}(t,x)\) takes values on the two-dimensional unit sphere \(\mathbb {S}^2\) and \(x \in \mathbb {R}\) (real line case) or \(x \in \mathbb {T}\) (periodic case). This an energy-critical Hamiltonian evolution equation recently introduced in Lenzmann and Schikorra (2017, arXiv:1702.05995v2), Zhou and Stone (Phys Lett A 379:2817–2825, 2015) which formally arises as an effective evolution equation in the classical and continuum limit of Haldane–Shastry quantum spin chains. We prove that the half-wave maps equation admits a Lax pair and we discuss some analytic consequences of this finding. As a variant of our arguments, we also obtain a Lax pair for the half-wave maps equation with target \(\mathbb {H}^2\) (hyperbolic plane).

     

Bis(trifluoroacetyl)phenols and their derivatives in reactions with selected phosphorus(III) compounds

The reactivity of bis(trifluoroacetyl)‐phenols toward selected λ³P derivatives was examined. In the case of dialkyl(isocyanato)phosphites, only one of both present trifluoracetyl moieties of substrate was involved. After addition of the phenolic OH moiety across the intermediary formed PN bond, tri‐, tetra‐, and pentacyclic α‐(trifluoromethyl)phosphoranes were produced in a highly diastereoselective reaction. An unusual deoxygenation of the intermediary hydroxyphosphorane was observed reacting 4‐methyl‐2,6‐bis‐(trifluoroacetyl)phenol with diethyl(trimethylsilyl)‐phosphite, and the subsequent hydrolysis gave γ‐hydroxy‐α‐(trifluoromethyl)phoshonate. On the contrary, during the reaction of the O‐silylated phenol with tris(trimethylsilyl)phosphite, a bis‐phosphonate was obtained that underwent heterocyclization to phosphono phosphole system. The mechanistic aspects of the studied reactions, as well as structural features of the synthesized compounds are discussed, based on the multinuclear NMR spectroscopy and X‐ray single crystal investigation data. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:474–482, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20451     

Total synthesis of the calphostins: application of fischer carbene complexes and thermodynamic control of atropisomers

The total syntheses of the potent protein kinase C inhibitors calphostins A, B, C, and D as well as a variety of structural analogues are reported. An aminobenzannulation reaction of an enantiopure chromium Fischer carbene complex is utilized to prepare a pentasubstituted naphthylamine. After optimization of side-chain substituents, conversion of the naphthylamine to an o-naphthoquinone was followed by biomimetic oxidative dimerization using trifluoroacetic acid and air yielding a 1:2 P/M mixture of atropisomeric perylenequinones. Thermal equilibration to a 3:1 P:M atropisomeric ratio and separation of the perylenequinones followed by side chain desymmetrization and functionalization led to the total synthesis of enantio- and diastereomerically pure calphostin C in only twelve steps from commercially available starting materials. In addition, calphostins A, B, D, and several structural analogues were prepared to evaluate biological activities.     

Synthesis,Reactivity and Structural Properties of Trifluoromethylphosphoranides

Phosphoranides are interesting hypervalent species which serve as model compounds for intermediates or transition states in nucleophilic substitution reactions at trivalent phosphorus substrates. Herein, the syntheses and properties of stable trifluoromethylphosphoranide salts are reported. [K(18-crown-6)][P(CF₃)₄], [K(18-crown-6)][P(CF₃)₃F], and [NMe₄][P(CF₃)₂F₂] were obtained by treatment of trivalent precursors with sources of CF₃⁻ or F⁻ units. These [P(CF₃)_4-nF_n]⁻ (n=0–2) salts exhibit fluorinating (n=1–2) or trifluoromethylating (n=0) properties, which is disclosed by studying their reactivity towards selected electrophiles. The solid-state structures of [K(18-crown-6)][P(CF₃)₄] and [K(18-crown-6)][P(CF₃)₃F] are ascertained by single crystal X-ray crystallography. The dynamics of these compounds are investigated by variable temperature NMR spectroscopy.     

Lewis Superacidic Tellurenyl Cation-Induced Electrophilic Activation of an Inert Carborane

The aryltellurenyl cation [2-(tBuNCH)C₆H₄Te]⁺, a Lewis super acid, and the weakly coordinating carborane anion [CB₁₁H₁₂]⁻, an extremely weak Brønsted acid (pK_a=131.0 in MeCN), form an isolable ion pair complex [2-(tBuNCH)C₆H₄Te][CB₁₁H₁₂], in which the Brønsted acidity (pK_a 7.4 in MeCN) of the formally hydridic B−H bonds is dramatically increased by more than 120 orders of magnitude. The electrophilic activation of B−H bonds in the carborane moiety gives rise to a proton transfer from boron to nitrogen at slightly elevated temperatures, as rationalized by the isolation of a mixture of the zwitterionic isomers 12- and 7-[2-(tBuN{H}CH)C₆H₄Te(CB₁₁H₁₁)] in ratios ranging from 62 : 38 to 80 : 20.     

Stable Borane Adducts of Alcoholates and Carboxylates

Six adducts of B(C₆F₅)₃ and archetypical alcoholates and carboxylates, were prepared and isolated as crystalline sodium crown ether salts, [Na(15‐crown‐5)][CH₃O · B(C₆F₅)₃] ( 1 ), [Na(15‐crown‐5)][CH₃CH₂O · B(C₆F₅)₃] ( 2 ), [Na(15‐crown‐5)][HCO₂ · B(C₆F₅)₃] ( 3 ), [Na(15‐crown‐5)][(H₃CCO₂ · B(C₆F₅)₃] ( 4 ), [Na(15‐crown‐5)][(F₃CCO₂ · B(C₆F₅)₃] ( 5 ), and [Na₂(15‐crown‐5)₃][C₂O₄ · 2 B(C₆F₅)₃] ( 6 ). All compounds were fully characterized by multinuclear NMR‐ and IR spectroscopy, ESI MS spectrometry, and X‐ray crystallography.     

B12H11-containing guanidinium derivatives by reaction of carbodiimides with H3N-B12H11(1−). A new method for connecting boron clusters to organic compounds

The reaction of B₁₂H₁₁NH₃(1−) with carbodiimides can form guanidinium salts containing the boron cluster. Depending on the side chains of the carbodiimide, these derivatives of the B₁₂H₁₂(2−) cluster can be uncharged or can carry an overall positive or negative charge. This reaction allows the preparation of derivatives with aliphatic side chains, in contrast to the acylation reaction of and the formation of Schiff bases, both of which are successful only with aromatic acid chlorides or aromatic, respectively, α,β-unsaturated aldehydes. The acylation of with benzoyl chloride gives an N-protonated form of an imidoacid, carrying a single overall charge.