@article{LiuMingFriedrichetal.2020,
  author    = {Liu, Xiaocui and Ming, Wenbo and Friedrich, Alexandra and Kerner, Florian and Marder, Todd B.},
  title     = {Copper-Catalyzed Triboration of Terminal Alkynes Using B\(_2\)pin\(_2\): Efficient Synthesis of 1,1,2-Triborylalkenes},
  series = {Angewandte Chemie International Edition},
  volume    = {59},
  journal   = {Angewandte Chemie International Edition},
  number    = {1},
  doi       = {10.1002/anie.201908466},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-206694},
  pages     = {304-309},
  year      = {2020},
  abstract  = {We report herein the catalytic triboration of terminal alkynes with B\(_2\)pin\(_2\) (bis(pinacolato)diboron) using readily available Cu(OAc)\(_2\) and P\(^n\)Bu\(_3\). Various 1,1,2-triborylalkenes, a class of compounds that have been demonstrated to be potential matrix metalloproteinase (MMP-2) inhibitors, were obtained directly in moderate to good yields. The process features mild reaction conditions, a broad substrate scope, and good functional group tolerance. This copper-catalyzed reaction can be conducted on a gram scale to produce the corresponding 1,1,2-triborylalkenes in modest yields. The utility of these products was demonstrated by further transformations of the C-B bonds to prepare gem -dihaloborylalkenes (F, Cl, Br), monohaloborylalkenes (Cl, Br), and trans -diaryldiborylalkenes, which serve as important synthons and have previously been challenging to prepare.},
  language  = {en}
}
@article{LenczykRoyOberdorfetal.2019,
  author    = {Lenczyk, Carsten and Roy, Dipak Kumar and Oberdorf, Kai and Nitsch, J{\"o}rn and Dewhurst, Rian D. and Radacki, Krzysztof and Halet, Jean-Fran{\c{c}}ois and Marder, Todd B. and Bickelhaupt, Matthias and Braunschweig, Holger},
  title     = {Toward Transition-Metal-Templated Construction of Arylated B\(_{4}\) Chains by Dihydroborane Dehydrocoupling},
  series = {Chemistry - A European Journal},
  volume    = {25},
  journal   = {Chemistry - A European Journal},
  number    = {72},
  doi       = {10.1002/chem.201904772},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-214324},
  pages     = {16544-16549},
  year      = {2019},
  abstract  = {The reactivity of a diruthenium tetrahydride complex towards three selected dihydroboranes was investigated. The use of [DurBH\(_{2}\)] (Dur=2,3,5,6-Me\(_{4}\)C\(_{6}\)H) and [(Me\(_{3}\)Si)\(_{2}\)NBH\(_{2}\)] led to the formation of bridging borylene complexes of the form [(Cp\(^{*}\)RuH)\(_{2}\)BR] (Cp\(^{*}\)=C\(_{5}\)Me\(_{5}\); 1 a: R=Dur; 1 b: R=N(SiMe\(_{3}\))\(_{2}\)) through oxidative addition of the B-H bonds with concomitant hydrogen liberation. Employing the more electron-deficient dihydroborane [3,5-(CF\(_{3}\))\(_{2}\)-C\(_{6}\)H\(_{3}\)BH\(_{2}\)] led to the formation of an anionic complex bearing a tetraarylated chain of four boron atoms, namely Li(THF)\(_{4}\)[(Cp\(^{*}\)Ru)\(_{2}\)B\(_{4}\)H\(_{5}\)(3,5-(CF\(_{3}\))\(_{2}\)C\(_{6}\)H\(_{3}\))\(_{4}\)] (4), through an unusual, incomplete threefold dehydrocoupling process. A comparative theoretical investigation of the bonding in a simplified model of 4 and the analogous complex nido-[1,2(Cp\(^{*}\)Ru)\(_{2}\)(μ-H)B\(_{4}\)H\(_{9}\)] (I) indicates that there appear to be no classical σ-bonds between the boron atoms in complex I, whereas in the case of 4 the B\(_{4}\) chain better resembles a network of three B-B σ bonds, the central bond being significantly weaker than the other two.},
  language  = {en}
}
@article{BudimanLorenzenLiuetal.2021,
  author    = {Budiman, Yudha P. and Lorenzen, Sabine and Liu, Zhiqiang and Radius, Udo and Marder, Todd B.},
  title     = {Base-Free Pd-Catalyzed C-Cl Borylation of Fluorinated Aryl Chlorides},
  series = {Chemistry - A European Journal},
  volume    = {27},
  journal   = {Chemistry - A European Journal},
  number    = {11},
  doi       = {10.1002/chem.202004648},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-225687},
  pages     = {3869 -- 3874},
  year      = {2021},
  abstract  = {Catalytic C-X borylation of aryl halides containing two ortho-fluorines has been found to be challenging, as most previous methods require stoichiometric amounts of base and the polyfluorinated aryl boronates suffer from protodeboronation, which is accelerated by ortho-fluorine substituents. Herein, we report that a combination of Pd(dba)2 (dba=dibenzylideneacetone) with SPhos (2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl) as a ligand is efficient to catalyze the C-Cl borylation of aryl chlorides containing two ortho-fluorine substituents. This method, conducted under base-free conditions, is compatible with the resulting di-ortho-fluorinated aryl boronate products which are sensitive to base.},
  language  = {en}
}
@article{LiuMingFriedrichetal.2020,
  author    = {Liu, Xiaocui and Ming, Wenbo and Friedrich, Alexandra and Marder, Todd B.},
  title     = {Kupfer-katalysierte Triborierung terminaler Alkine mit B2pin2: Effiziente Synthese von 1,1,2-Triborylalkenen},
  series = {Angewandte Chemie},
  volume    = {132},
  journal   = {Angewandte Chemie},
  number    = {1},
  doi       = {10.1002/ange.201908466},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-219699},
  pages     = {311-316},
  year      = {2020},
  abstract  = {Wir berichten {\"u}ber die katalytische Triborierung terminaler Alkine mit B\(_2\)pin\(_2\) (Bis-(pinakolato)-dibor) unter Verwendung von einfach zug{\"a}nglichem Cu(OAc)\(_2\) und P\(^n\)Bu\(_3\). Verschiedene 1,1,2-Triborylalkene, eine Verbindungsklasse mit potentieller Funktion als Matrix-Metallo-Proteinase(MMP-2)-Inhibitor, werden direkt in m{\"a}ßigen bis guten Ausbeuten erhalten. Das Verfahren zeichnet sich durch milde Reaktionsbedingungen, ein breites Substratspektrum und eine gute Vertr{\"a}glichkeit gegen{\"u}ber funktionellen Gruppen aus. Diese Cu-katalysierte Reaktion kann im Gramm-Maßstab durchgef{\"u}hrt werden und liefert die entsprechenden 1,1,2-Triborylalkene in m{\"a}ßigen Ausbeuten. Die Verwendung solcher Verbindungen wird anhand weiterer Transformationen der C-B-Bindungen zur Darstellung eines geminalen Dihalogenborylalkens (F, Cl, Br), eines Monohalogendiborylalkens (Cl, Br) und eines trans-Diaryldiborylalkens demonstriert, welche bedeutende Synthesebausteine darstellen und bisher nur schwer zug{\"a}nglich waren.},
  language  = {de}
}
@article{LenczykRoyNitschetal.2019,
  author    = {Lenczyk, Carsten and Roy, Dipak Kumar and Nitsch, J{\"o}rn and Radacki, Krzysztof and Rauch, Florian and Dewhurst, Rian D. and Bickelhaupt, F. Matthias and Marder, Todd B. and Braunschweig, Holger},
  title     = {Steric Effects Dictate the Formation of Terminal Arylborylene Complexes of Ruthenium from Dihydroboranes},
  series = {Chemistry - A European Journal},
  volume    = {25},
  journal   = {Chemistry - A European Journal},
  number    = {59},
  issn      = {1521-3765},
  doi       = {10.1002/chem.201902890},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-219537},
  pages     = {13566-13571},
  year      = {2019},
  abstract  = {The steric and electronic properties of aryl substituents in monoaryl borohydrides (Li[ArBH\(_3\)]) and dihydroboranes were systematically varied and their reactions with [Ru(PCy\(_3\))\(_2\)HCl(H\(_2\))] (Cy: cyclohexyl) were studied, resulting in bis(σ)-borane or terminal borylene complexes of ruthenium. These variations allowed for the investigation of the factors involved in the activation of dihydroboranes in the synthesis of terminal borylene complexes. The complexes were studied by multinuclear NMR spectroscopy, mass spectrometry, X-ray diffraction analysis, and density functional theory (DFT) calculations. The experimental and computational results suggest that the ortho-substitution of the aryl groups is necessary for the formation of terminal borylene complexes.},
  language  = {en}
}
@article{LiuMingLuoetal.2020,
  author    = {Liu, Xiaocui and Ming, Wenbo and Luo, Xiaoling and Friedrich, Alexandra and Maier, Jan and Radius, Udo and Santos, Webster L. and Marder, Todd B.},
  title     = {Regio- and Stereoselective Synthesis of 1,1-Diborylalkenes via Br{\o}nsted Base-Catalyzed Mixed Diboration of Alkynyl Esters and Amides with BpinBdan},
  series = {European Journal of Organic Chemistry},
  volume    = {2020},
  journal   = {European Journal of Organic Chemistry},
  number    = {13},
  doi       = {10.1002/ejoc.202000128},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-214728},
  pages     = {1941 -- 1946},
  year      = {2020},
  abstract  = {The NaOtBu-catalyzed mixed 1,1-diboration of terminal alkynes using the unsymmetrical diboron reagent BpinBdan (pin = pinacolato; dan = 1,8-diaminonaphthalene) proceeds in a regio- and stereoselective fashion affording moderate to high yields of 1,1-diborylalkenes bearing orthogonal boron protecting groups. It is applicable to gram-scale synthesis without loss of yield or selectivity. The mixed 1,1-diborylalkene products can be utilized in Suzuki-Miyaura cross-coupling reactions which take place selectivly at the C-B site. DFT calculations suggest the NaOtBu-catalyzed mixed 1,1-diboration of alkynes occurs through deprotonation of the terminal alkyne, stepwise addition of BpinBdan to the terminal carbon followed by protonation with tBuOH. Experimentally observed selective formation of (Z)-diborylalkenes is supported by our theoretical studies.},
  language  = {en}
}
@article{RauchEndresFriedrichetal.2020,
  author    = {Rauch, Florian and Endres, Peter and Friedrich, Alexandra and Sieh, Daniel and H{\"a}hnel, Martin and Krummenacher, Ivo and Braunschweig, Holger and Finze, Maik and Ji, Lei and Marder, Todd B.},
  title     = {An Iterative Divergent Approach to Conjugated Starburst Borane Dendrimers},
  series = {Chemistry - A European Journal},
  volume    = {26},
  journal   = {Chemistry - A European Journal},
  number    = {57},
  doi       = {10.1002/chem.202001985},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-218345},
  pages     = {12951 -- 12963},
  year      = {2020},
  abstract  = {Using a new divergent approach, conjugated triarylborane dendrimers were synthesized up to the 2nd generation. The synthetic strategy consists of three steps: 1) functionalization, via iridium catalyzed C-H borylation; 2) activation, via fluorination of the generated boronate ester with K[HF\(_{2}\)] or [N(nBu\(_{4}\))][HF\(_{2}\)]; and 3) expansion, via reaction of the trifluoroborate salts with aryl Grignard reagents. The concept was also shown to be viable for a convergent approach. All but one of the conjugated borane dendrimers exhibit multiple, distinct and reversible reduction potentials, making them potentially interesting materials for applications in molecular accumulators. Based on their photophysical properties, the 1st generation dendrimers exhibit good conjugation over the whole system. However, the conjugation does not increase further upon expansion to the 2nd generation, but the molar extinction coefficients increase linearly with the number of triarylborane subunits, suggesting a potential application as photonic antennas.},
  language  = {en}
}
@article{FergerBergerRauchetal.2021,
  author    = {Ferger, Matthias and Berger, Sarina M. and Rauch, Florian and Sch{\"o}nitz, Markus and R{\"u}he, Jessica and Krebs, Johannes and Friedrich, Alexandra and Marder, Todd B.},
  title     = {Synthesis of Highly Functionalizable Symmetrically and Unsymmetrically Substituted Triarylboranes from Bench-Stable Boron Precursors},
  series = {Chemistry—A European Journal},
  volume    = {27},
  journal   = {Chemistry—A European Journal},
  number    = {35},
  doi       = {10.1002/chem.202100632},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-256827},
  pages     = {9094-9101},
  year      = {2021},
  abstract  = {A novel and convenient methodology for the one-pot synthesis of sterically congested triarylboranes by using bench-stable aryltrifluoroborates as the boron source is reported. This procedure gives systematic access to symmetrically and unsymmetrically substituted triarylboranes of the types BAr\(_{2}\)Ar' and BArAr'Ar'', respectively. Three unsymmetrically substituted triarylboranes as well as their iridium-catalyzed C-H borylation products are reported. These borylated triarylboranes contain one to three positions that can subsequently be orthogonally functionalized in follow-up reactions, such as Suzuki-Miyaura cross-couplings or Sonogashira couplings.},
  language  = {en}
}
@article{JosSzwetkowskiSlebodnicketal.2022,
  author    = {Jos, Swetha and Szwetkowski, Connor and Slebodnick, Carla and Ricker, Robert and Chan, Ka Lok and Chan, Wing Chun and Radius, Udo and Lin, Zhenyang and Marder, Todd B. and Santos, Webster L.},
  title     = {Transition Metal-Free Regio- and Stereo-Selective trans Hydroboration of 1,3-Diynes: A Phosphine-Catalyzed Access to (E)-1-Boryl-1,3-Enynes},
  series = {Chemistry - A European Journal},
  volume    = {28},
  journal   = {Chemistry - A European Journal},
  number    = {63},
  doi       = {10.1002/chem.202202349},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-293784},
  year      = {2022},
  abstract  = {We report a transition metal-free, regio- and stereo-selective, phosphine-catalyzed method for the trans hydroboration of 1,3-diynes with pinacolborane that affords (E)-1-boryl-1,3-enynes. The reaction proceeds with excellent selectivity for boron addition to the external carbon of the 1,3-diyne framework as unambiguously established by NMR and X-ray crystallographic studies. The reaction displays a broad substrate scope including unsymmetrical diynes to generate products in high yield (up to 95 \%). Experimental and theoretical studies suggest that phosphine attack on the alkyne is a key process in the catalytic cycle.},
  language  = {en}
}
@article{BanKaračićTomićetal.2021,
  author    = {Ban, Željka and Karačić, Zrinka and Tomić, Sanja and Amini, Hashem and Marder, Todd B. and Piantanida, Ivo},
  title     = {Triarylborane dyes as a novel non-covalent and non-inhibitive fluorimetric markers for DPP III enzyme},
  series = {Molecules},
  volume    = {26},
  journal   = {Molecules},
  number    = {16},
  issn      = {1420-3049},
  doi       = {10.3390/molecules26164816},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-245046},
  year      = {2021},
  abstract  = {Novel dyes were prepared by simple "click CuAAC" attachment of a triarylborane-alkyne to the azide side chain of an amino acid yielding triarylborane dye 1 which was conjugated with pyrene (dye 2) forming a triarylborane-pyrene FRET pair. In contrast to previous cationic triarylboranes, the novel neutral dyes interact only with proteins, while their affinity to DNA/RNA is completely abolished. Both the reference triarylborane amino acid and triarylborane-pyrene conjugate bind to BSA and the hDPP III enzyme with high affinities, exhibiting a strong (up to 100-fold) fluorescence increase, whereby the triarylborane-pyrene conjugate additionally retained FRET upon binding to the protein. Furthermore, the triarylborane dyes, upon binding to the hDPP III enzyme, did not impair its enzymatic activity under a wide range of experimental conditions, thus being the first non-covalent fluorimetric markers for hDPP III, also applicable during enzymatic reactions with hDPP III substrates.},
  language  = {en}
}