Cycloaddition Reactions of an Active Cyclic Phosphane/Borane Pair with Alkenes,Alkynes, and Carbon Dioxide

The active six-membered cyclo-FLP 6 undergoes a rapid P/B addition reaction to carbon dioxide. At elevated temperature, the resulting heterobicyclo[2.2.2]octane derived product 7 undergoes ring opening and equilibrates with the cyclotetramer (7)₄ . In the large macrocyclic structure, four monomeric six-membered cyclo-FLP units are connected by four CO₂ molecules to form the supramolecular ring system. The P/B cyclo-FLP 6 undergoes a variety of additional cycloaddition reactions.     

Switching the Switch: Ligand Induced Disulfide Formation in HDAC8

Human histone deacetylase 8 is a well-recognized target for T-cell lymphoma and particularly childhood neuroblastoma. PD-404,182 was shown to be a selective covalent inhibitor of HDAC8 that forms mixed disulfides with several cysteine residues and is also able to transform thiol groups to thiocyanates. Moreover, HDAC8 was shown to be regulated by a redox switch based on the reversible formation of a disulfide bond between cysteines Cys₁₀₂ and Cys₁₅₃. This study on the distinct effects of PD-404,182 on HDAC8 reveals that this compound induces the dose-dependent formation of intramolecular disulfide bridges. Therefore, the inhibition mechanism of HDAC8 by PD-404,182 involves both, covalent modification of thiols as well as ligand mediated disulfide formation. Moreover, this study provides a deep molecular insight into the regulation mechanism of HDAC8 involving several cysteines with graduated capability to form reversible disulfide bridges.     

Metal‐Catalyzed “On‐Demand” Production of Carbonyl Sulfide from Carbon Monoxide and Elemental Sulfur

The group 6 molybdenum(II) cyclopentadienyl amidinate (CPAM) bis(carbonyl) complex [Cp*Mo{N(iPr)C(Ph)N(iPr)}(CO)₂] (Cp*=η⁵‐C₅Me₅) serves as a precatalyst for the high‐yielding photocatalytic production of COS from CO and S₈ under near‐ambient conditions (e.g., 10 psi, 25 °C). Further documented is the isolation and structural characterization of several key transition‐metal intermediates which collectively support a novel molybdenum(IV)‐based catalytic cycle as being operative. Finally, in the presence of an excess amount of a primary amine, it is demonstrated that this catalytic system can be successfully used for the “on‐demand” generation and utilization of COS as a chemical reagent for the synthesis of ureas.     

Functionalization of Intramolecular Frustrated Lewis Pairs by 1,1‐Carboboration with Conjugated Enynes

The vicinal P/B frustrated Lewis pair (FLP) Mes₂PCH₂CH₂B(C₆F₅)₂ undergoes 1,1‐carboboration reactions with the Me₃Si‐substituted enynes to give ring‐enlarged functionalized C₃‐bridged P/B FLPs. These serve as active FLPs in the activation of dihydrogen to give the respective zwitterionic [P]H⁺/[B]H^? products. One such product shows activity as a metal‐free catalyst for the hydrogenation of enamines or a bulky imine. The ring‐enlarged FLPs contain dienylborane functionalities that undergo “bora‐Nazarov”‐type ring‐closing rearrangements upon photolysis. A DFT study had shown that the dienylborane cyclization of such systems itself is endothermic, but a subsequent C₆F₅ migration is very favorable. Furthermore, substituted 2,5‐dihydroborole products are derived from cyclization and C₆F₅ migration from the photolysis reaction. In the case of the six‐membered annulation product, a subsequent stereoisomerization reaction takes place and the resultant compound undergoes a P/B FLP 1,2‐addition reaction with a terminal alkyne with rearrangement.     

Fluorene-containing tetraphenylethylene molecules as lasing materials

A series of star-shaped oligofluorene molecules, each containing a TPE core, have been specifically designed and produced to show effective aggregation-induced emission (AIE). Each molecule differs either in the number of fluorene units within the arms (e.g., 1 or 4, compounds 4 and 5 ), or the terminal group positioned at the end of each arm (e.g., H, TMS, or TPA, compounds 4 , 6 , and 7 ). Although they are all poor emitters in solution phase they become efficient yellow-green luminogens in the condensed state. Their AIE properties were investigated in THF/H₂O mixtures, with each molecule exhibiting a clear emission enhancement at specific water contents. An all-organic distributed feedback (DFB) laser was fabricated using compound 4 as the gain material and exhibited an average threshold energy fluence of 60 ± 6 μJ/cm² and emission in the green region. Furthermore, piezofluorochromism studies on a thin film of this material displayed a linear dependence of the amplified spontaneous emission (ASE) peak position on applied pressure, indicating potential applications as lasing-based pressure sensors. © 2016 The Authors. Journal of Polymer Science Part A: Polymer Chemistry Published by Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 734–746     

Frustrated Lewis Pair Chemistry: Searching for New Reactions

Frustrated Lewis pair chemistry has taken a steep development in the recent years. It offers possibilities of developing new variants of known reactions and of finding new chemical transformations. This is demonstrated and described by the recently developed FLP‐formylborane chemistry, which has led to the formation of the unique (η²‐formylborane)FLP adducts and opened a way of preparing a genuine formylborane compound, which shows an interesting follow‐up chemistry. FLPs have helped finding phosphorus analogues of the enamine Stork reaction and the Claisen reaction. These reactions lead to new organophosphorus compounds and they make new phosphane/borane systems available. P/B FLPs add to a variety of small main group element oxides. They undergo 1,2‐addition reactions to CO₂, SO₂ and other heterocumulenes and they feature unique 1,1‐addition reactions to carbon monoxide, to isonitriles and even to nitric oxide (NO), the latter yielding examples of a new class of persistent nitroxide radicals, the FLPNO nitroxyls. Eventually, some remarkable radical reactions of FLPs and related compounds are briefly mentioned.