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Reductively Stable Hydrogen-Bonding Ligands Featuring Appended CF2-H Units

We present the development of ligands featuring the unconventional hydrogen bond donor, -CF2H, within a metal’s secondary coordination sphere. When metalated with palladium, o-CF2H-functionalized 1,10-phenanthroline provides highly directed H-bonding interactions with Pd-coordinated substrates. Spectroscopic and computational analyses with a series of X-type ligand acceptors (-F, -Cl, -Br, -OR) establish the H-bonding interaction strength for the -CF2H group (?3 kcal/mol). The synthesis of Pd0/Ni0 complexes and subsequent coupling (Ni) highlight the unique reductive and base compatibility of the -CF2H hydrogen bond donor group.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Aggregation Strength Tuning in Difluorobenzoxadiazole-Based Polymeric Semiconductors for High-Performance Thick-Film Polymer Solar Cells

High-performance polymer solar cells (PSCs) with thick active layers are essential for large-scale production. Polymer semiconductors exhibiting a temperature-dependent aggregation property offer great advantages toward this purpose. In this study, three difluorobenzoxadiazole (ffBX)-based donor polymers, PffBX-T, PffBX-TT, and PffBX-DTT, were synthesized, which contain thiophene (T), thieno[3,2-b]thiophene (TT), and dithieno[3,2-b:2?,3?-d]thiophene (DTT) as the pi-spacers, respectively. Temperature-dependent absorption spectra reveal that the aggregation strength increases in the order of PffBX-T, PffBX-TT, and PffBX-DTT as the pi-spacer becomes larger. PffBX-TT with the intermediate aggregation strength enables well-controlled disorder-order transition in the casting process of blend film, thus leading to the best film morphology and the highest performance in PSCs. Thick-film PSCs with an average power conversion efficiency (PCE) of 8.91% and the maximum value of 9.10% are achieved using PffBX-TT:PC71BM active layer with a thickness of 250 nm. The neat film of PffBX-TT also shows a high hole mobility of 1.09 cm2 V-1 s-1 in organic thin-film transistors. When PffBX-DTT and PffBX-T are incorporated into PSCs utilizing PC71BM acceptor, the average PCE decreases to 6.54 and 1.33%, respectively. The performance drop mainly comes from reduced short-circuit current, as a result of nonoptimal blend film morphology caused by a less well-controlled film formation process. A similar trend was also observed in nonfullerene type thick-film PSCs using IT-4F as the electron acceptor. These results show the significance of polymer aggregation strength tuning toward optimal bulk heterojunction film morphology using ffBX-based polymer model system. The study demonstrates that adjusting pi-spacer is an effective method, in combination with other important approaches such as alkyl chain optimization, to generate high-performance thick-film PSCs which are critical for practical applications.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Cyano substituted (Z)-(thienylmethylene)-2-indolone as a new building block for near-IR absorbing polymers

A new electron withdrawing monomer, cyano substituted (Z)-(thienylmethylene)-2-indolone (TEI(CN)) has been synthesized and polymerized with different donors to give three alternating donor/acceptor conjugated polymers. The cyano substituted polymers showed significantly reduced LUMO energy levels and small optical bandgaps compared with un-substituted polymer. The optical absorptions of new polymers mainly appeared in NIR range, peaked at 700?800 nm. With strong electron donor EDOT, the polymer, PTEI(CN)-EDOT showed most of its absorption in NIR region (>700 nm). The inverted bulk hetero-junction polymer solar cells based on two of the new polymers were fabricated and tested.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Synthesis and Structure-Activity Relationships of 1-Aryl-beta-carbolines as Affinity Probes for the 5-Hydroxytryptamine Receptor

Simple beta-carbolines have been shown to bind several protein receptors that are important for signaling in the central nervous system. Herein, we expand our previous efforts into the synthesis and biological activity of these heterocycles by studying their neuropharmacological activity. A diverse set of 1-aryl-beta-carbolines has been synthesized via Suzuki cross-coupling from a common triflate precursor and several substituted aryl boronic acids. The resulting 26-member library was subjected to primary screening at 10 muM for activity against 40 protein receptors implicated in brain signaling. The Ki was subsequently determined for several lead structures. The most potent activity, as low as 100 nM, was found against the 5-hydroxytryptamine subtype-2 family of receptors. In-depth structure-activity relationships for these synthetic beta-carbolines have been developed, which point to the importance of a 3-indolyl substituent attached to the 1-position of the beta-carboline and a 6-methoxy substituent on the beta-carboline core.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Capturing a ghost. synthesis and structural characterization of Pd(dba)[P(o -Tol)3]2

In an effort to improve upon a literature synthesis of bis[tris(o-tolyl) phosphine]palladium(0) (1) from tris(o-tolyl)phosphine and Pd 2(dba)3, we instead isolated a new compound which proved to have the composition Pd(dba)[P(o-Tol)3]2 (2), upon analysis by X-ray crystallography. While this is not the first known palladium compound containing both dba and phosphine ligands, it is, to our knowledge, the first containing dba and tris(o-tolyl)phosphine. This is significant, because mixtures of Pd2(dba)3 and tris(o-tolyl)phosphine are routinely used in cross-coupling protocols, and palladium complexes containing dba and tris(o-tolyl)phosphine have been cited as intermediates in organometallic and polymerization reactions. The most interesting crystallographic parameter for 2 is an abnormally long Pd-P bond length of 2.388(1) A, which we believe is the cause of this complex’s metastability. We also present an alternative synthesis of 1 that does not require a large excess of phosphine.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Highly stereoselective carbon-carbon bond-forming reactions on cyclopropane rings using 1-(methoxycarbonyl)cyclopropylzinc bromides

Highly stereoselective Reformatsky reaction and Pd-catalyzed arylation using 1-(alkoxycarbonyl)cyclopropylzinc bromide proceeded to give the trans-adduct as the major product in good to high yields with good to excellent stereoselectivities.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Oxindole derivatives, preparation thereof and therapeutic use in the treatment of AMPK-related diseases

The present invention relates to compounds corresponding to formula (I): Process for the preparation thereof and therapeutic use thereof. The compounds are modulators of the activity of AMP-activated protein kinase (AMPK) and are useful for treating e.g. diabetes and obesity.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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An intramolecular para-phenolic allylation free radical cyclization strategy for the synthesis of alkaloids and terpenes with spiro[4.5]decane architectures

A Tsuji-Trost variant of the Winstein-Masamune reaction has been investigated for the synthesis of the AC spirocyclic ring system 9 bearing a quaternary carbon found in the fawcettimine type Lycopodium alkaloids magellanine 1 and lycojaponicumin B 2 and cyclopiane diterpenes such as conidiogenone 3. Annulation of the B ring for the synthesis of tricyclic ABC cores was demonstrated utilizing a 5-exo-trig free radical cyclization of a primary carbon radical onto a cyclohexadienone generated with tri-n-butylgermanium hydride (9 ? 11).

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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(1-Bromovinyl)-MIDA boronate: A readily accessible and highly versatile building block for small molecule synthesis Dedicated to Professor Paul Wender with deepest admiration on his receipt of the 2012 Tetrahedron Prize for Creativity in Organic Chemistry

Iterative cross-coupling represents a potentially general approach for the simple, efficient, and flexible construction of a wide range of functional small molecules. In this context, (1-bromovinyl)-N-methyliminodiacetic acid (MIDA) boronate is a very useful building block for small molecule synthesis. This compound can serve as a starting material for the preparation of a wide range of 1,1-disubstituted olefin-containing MIDA boronates. This compound can also be used for the iterative cross-coupling-based synthesis of various 1,1-disubstituted olefin-containing targets. Collectively, these results contribute to the expanding generality of the MIDA boronate platform.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Effect of chlorination and fluorination of benzothiadiazole on the performance of polymer solar cells

In order to explore the effects of chlorine and fluorine on photophysical properties and the differences, in this work, we synthesized five new polymers, P1?P5, in which benzo[1,2-b:4,5-b]dithiophene as the electron donating and benzothiadiazole as electron withdrawing. Analysis of these five polymers showed that the introduction of Cl and F atoms can deeper the highest occupied molecular orbital of these polymers and enhance the absorption of light by the species, thereby improving Voc and Jsc. Chlorination has a stronger ability to reduce energy levels and broaden the absorption spectrum compared to fluorination. Among them, P2 showed an efficiency of 4.08% with Jsc of 11.28 mA/cm2, Voc of 0.79 V, and fill factor (FF) of 0.45. Since chlorination is easier than fluorination in terms of synthesis, it is advantageous for practical applications. Therefore, we think that chlorination should not be ignored when designing high efficiency photovoltaic materials, especially when their fluorinated counterparts have proven to have good properties.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method