170160-98-2Relevant academic research and scientific papers
Strain-Promoted Double Azide Addition to Octadehydrodibenzo[12]annulene Derivatives
Fukushima, Satomi,Ashizawa, Minoru,Kawauchi, Susumu,Michinobu, Tsuyoshi
, (2019)
Octadehydrodibenzo[12]annulenes (DBAs), readily available by the oxidative acetylenic coupling of 1,2-diethynylbenzene derivatives, were reacted with organic azides. As compared to the well-known strain-promoted azide-alkyne cycloaddition (SpAAC) of 5,6,11,12-tetradehydrodibenzo[a,e][8]annulene, the reactivity of the DBA alkynes was lower due to the lower strain energy. However, the regioselective double azide addition occurred without any side reactions under mild conditions, yielding bis-triazole products. The structures of the products were confirmed by an X-ray crystal structure analysis, and the reaction mechanism was studied by 1H-NMR spectroscopy and computational studies. It was also found that the DBAs were hardly fluorescent, while the bis-triazole products showed a green fluorescence with quantum yields up to 5.1 %. Finally, the new strain-promoted double azide addition to the DBAs was used for step-growth polymerization, successfully producing a high molecular weight triazole polymer.
Synthesis of arenediynes via the vinylidenecarbene-acetylene rearrangement
Sahu, Bichismita,Namboothiri, Irishi N.N.,Persky, Rachel
, p. 2593 - 2597 (2005)
A convenient method for the two-step synthesis of arenediynes from 1,2-arenedialdehydes is reported. Dibromomethylenation of dialdehydes under Corey-Fuchs conditions (CBr4, Ph3P, Zn) provides the tetrabromides in excellent yields. Treatment of the tetrabromides with n-BuLi or LDA affords 3,4-unsaturated 1,5-diynes, the key structural moiety present in several naturally occurring antitumour antibiotics, in varying yields. The key intermediates in these transformations appear to be vinylidenecarbenes or carbenoids, generated in situ via metal-halogen exchange and elimination.
CO extrusion in homogeneous gold catalysis: Reactivity of gold acyl species generated through water addition to gold vinylidenes
Bucher, Janina,St?sser, Tim,Rudolph, Matthias,Rominger, Frank,Hashmi, A. Stephen K.
supporting information, p. 1666 - 1670 (2015/01/30)
Herein, we describe a new gold-catalyzed decarbonylative indene synthesis. Synergistic σ,π-activation of diyne substrates leads to gold vinylidene intermediates, which upon addition of water are transformed into gold acyl species, a type of organogold compound hitherto only scarcely reported. The latter are shown to undergo extrusion of CO, an elementary step completely unknown for homogeneous gold catalysis. By tuning the electronic and steric properties of the starting diyne systems, this new reactivity could be exploited for the synthesis of indene derivatives in high yields.
Gold-catalyzed hydroarylating cyclization of 1,2-Bis(2-iodoethynyl)benzenes
N?sel, Pascal,Müller, Vanessa,Mader, Steffen,Moghimi, Setareh,Rudolph, Matthias,Braun, Ingo,Rominger, Frank,Hashmi, A. Stephen K.
supporting information, p. 500 - 506 (2015/03/05)
1,5-Diynes bearing halogen-substituted alkynes were synthesized and converted in the presence of a gold catalyst. In contrast to the corresponding hydroarylating aromatization reaction with terminal alkynes, a totally different reaction mode was observed.
Grignard reagent/CuI/LiCl-mediated stereoselective cascade addition/cyclization of diynes: A novel pathway for the construction of 1-methyleneindene derivatives
Li, De-Yao,Wei, Yin,Shi, Min
supporting information, p. 15682 - 15688 (2013/11/19)
Diynes containing a cyclopropane group smoothly undergo a novel intramolecular and stereoselective cascade addition/cyclization reaction to produce the corresponding 1-methyleneindene derivatives in moderate to good yields. This interesting transformation is mediated by Grignard reagent/CuI with LiCl as an additive under mild conditions. The obtained product can easily be further functionalized through cyclopropyl ring opening. A plausible reaction mechanism has also been presented on the basis of deuterium labeling and control experiments. Diyne cyclization: Diynes containing a cyclopropane group undergo a novel intramolecular and stereoselective cascade addition/cyclization reaction to produce the corresponding 1-methyleneindene derivatives (see scheme). The transformation proceeds under mild conditions and is promoted by a combination of Grignard reagent Copyright
The trisubstituted-triazole approach to extended functional naphthalocyanines
Jurí?ek, Michal,Stout, Kathleen,Kouwer, Paul H.J.,Rowan, Alan E.
experimental part, p. 898 - 907 (2012/03/26)
Recently, a novel modular approach to octatriazole-derived phthalocyanines (Pcs; 1) was developed and optimized in our group; herein, the pool of the functional Pc materials was expanded for an additional candidate (2), a fused derivative of 1. Compared w
Ligand bridging-angle-driven assembly of molecular architectures based on quadruply bonded Mo-Mo dimers
Li, Jian-Rong,Yakovenko, Andrey A.,Lu, Weigang,Timmons, Daren J.,Zhuang, Wenjuan,Yuan, Daqiang,Zhou, Hong-Cai
supporting information; experimental part, p. 17599 - 17610 (2011/02/26)
A systematic exploration of the assembly of Mo2(O 2C-)4-based metal-organic molecular architectures structurally controlled by the bridging angles of rigid organic linkers has been performed. Twelve bridging dicarboxylate ligands were designed to be of different sizes with bridging angles of 0, 60, 90, and 120° while incorporating a variety of nonbridging functional groups, and these ligands were used as linkers. These dicarboxylate linkers assemble with quadruply bonded Mo-Mo clusters acting as nodes to give 13 molecular architectures, termed metal-organic polygons/polyhedra with metal cluster node arrangements of a linear shape, triangle, octahedron, and cuboctahedron/anti-cuboctahedron. The syntheses of these complexes have been optimized and their structures determined by single-crystal X-ray diffraction. The results have shown that the shape and size of the resulting molecular architecture can be controlled by tuning the bridging angle and size of the linker, respectively. Functionalization of the linker can adjust the solubility of the ensuing molecular assembly but has little or no effect on the geometry of the product. Preliminary gas adsorption, spectroscopic, and electrochemical properties of selected members were also studied. The present work is trying to enrich metal-containing supramolecular chemistry through the inclusion of well-characterized quadruply bonded Mo-Mo units into the structures, which can widen the prospect of additional electronic functionality, thereby leading to novel properties.
Synthesis of dicarboxylate "C-clamp" 1,2-diethynylarene compounds as potential transition-metal ion hosts
Reisner, Erwin,Lippard, Stephen J.
, p. 156 - 163 (2008/09/18)
We report an efficient convergent synthesis of a new type of C-clamp ligand with a 1,2-diethynylarene scaffold involving a chelate host capable of binding a guest molecule in its endo-dicarboxylate pocket. The chemistry involves a combination of palladium-catalyzed Sonogashira, Heck, and Suzuki cross-coupling reactions. The compounds 2,3-bis[2-(2′-carboxybiphenyl-4-yl)ethynyl] triptycene and 4,5-bis[2-(2′-carboxybiphenyl-4-yl)ethynyl]veratrole and their 2′-carboxy-m-terphenyl-4-yl analogues were designed as dinucleating ligands to assemble carboxylate-bridged transition-metal complexes with a windmill geometry. The X-ray crystal structure of one such C-clamp compound containing co-crystallized water molecules reveals strong hydrogen bonds of the aqua guest to the endo-oriented carboxylic acid entities of the C-clamp host. In addition, two syn-N-donor ligands were prepared as a synthetic scaffold to mimic the geometric arrangement of N-donor atoms in carboxylate-bridged dinuclear proteins. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
Synthetic and mechanistic investigations on the rearrangement of 2,3-unsaturated 1,4-bis(alkylidene)carbenes to enediynes
Sahu, Bichismita,Muruganantham, Rajendran,Namboothiri, Irishi N. N.
, p. 2477 - 2489 (2008/03/13)
The synthesis of 3,4-ene-1,5-diynes, the key structural moiety present in several naturally occurring antitumor antibiotics, from 1,2-enedialdehydes under two different experimental conditions is reported. One method involves the dibromomethylenation of dialdehydes under Corey-Fuchs conditions (CBr 4, Ph3P, and Zn) and treatment of the resulting tetrabromides with nBuLi or LDA to afford enediynes. The second method involves a base-mediated reaction of enedialdehydes with diethyl (1-diazo-2-oxopropyl) phosphonate (Bestmann-Ohira reagent) and subsequent transformation of the bis(diazo) compounds generated in situ to enediynes. While the transformation of bis(diazo) compounds to enediynes could take place exclusively through alkylidene-carbenes, generated in situ by geminal elimination of N2, an alternative pathway, involving the vicinal elimination of HBr to afford an intermediate bromoalkyne and its subsequent metal-halogen exchange and protonation during workup, exists for the bis(dibromoalkylidenes). However, our deuterium-labeling experiments with a model substrate, deuterated p-methoxybenzylidene dibromide, established the predominance of the alkylidenecarbenes, generated in situ by metal-halogen exchange and elimination, for this substrate and, by analogy, for the tetrabromides as well. The scope of this novel methodology was extended to the synthesis of various heteroatom-based (S, Se, and P) enediynes by quenching the acetylides with suitable electrophiles. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.
Soluble dipolar dendrimers with peripheral sulfone groups
Lu, Meng,Pan, Yongchun,Peng, Zhonghua
, p. 7903 - 7906 (2007/10/03)
A dipolar dendron based on meta and para linked poly(phenyl acetylene)s with eight electron donor-acceptor pairs in direct conjugations is synthesized through a convergent approach.
