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《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(1):308-320
Palladium‐catalyzed sixfold coupling of hexabromobenzene ( 20 ) with a variety of alkenylboronates and alkenylstannanes provided hexaalkenylbenzenes 1 in up to 73 % and 16 to 41 % yields, respectively. In some cases pentaalkenylbenzenes 21 were isolated as the main products (up to 75 %). Some functionally substituted hexaalkenylbenzene derivatives containing oxygen or sulfur atoms in each of their six arms have also been prepared (16 to 24 % yield). The sixfold coupling of the less sterically encumbered 2,3,6,7,10,11‐hexabromotriphenylene ( 24 ) gave the desired hexakis(3,3‐dimethyl‐1‐butenyl)triphenylene ( 25 ) in 93 % yield. The first successful cross‐coupling reaction of octabromonaphthalene ( 26 ) gave octakis‐(3,3‐dimethyl‐1‐butenyl)naphthalene ( 27 ) in 21 % yield. Crystal structure analyses disclose that, depending on the nature of the substituents, the six arms are positioned either all on the same side of the central benzene ring as in 1 a and 1 i , making them nicely cup‐shaped molecules, or alternatingly above and below the central plane as in 1 h and 23 . In 27 , the four arms at C‐1,4,6,7 are down, while the others are up, or vice versa. Upon catalytic hydrogenation, 1 a yielded 89 % of hexakis(tert‐butylethyl)benzene ( 23 ). Some efficient accesses to alkynes with sterically demanding substituents are also described. Elimination of phosphoric acid from the enol phosphate derived from the corresponding methyl ketones gave 1‐ethynyladamantane ( 3 b , 62 % yield), 1‐ethynyl‐1‐methylcyclohexane ( 3 c , 85 %) and 3,3‐dimethylpentyne ( 3 e , 65 %). 1‐(Trimethylsilyl)ethynylcyclopropane ( 7 ) was used to prepare 1‐ethynyl‐1‐methylcyclopropane ( 3 d ) (two steps, 64 % overall yield). The functionally substituted alkynes 3 f – h were synthesized in multistep sequences starting from the propargyl chloride 11 , which was prepared in high yields from the dimethylpropargyl alcohol 10 (94 %). The alkenylstannanes 19 were prepared by hydrostannation of the corresponding alkynes in moderate to high yields (42–97 %), and the alkenylboronates 2 and 4 by hydroboration with catecholborane (27–96 % yield) or pinacolborane (26–69 % yield). 相似文献
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Cover Picture: Metal‐ and Reagent‐Free Highly Selective Anodic Cross‐Coupling Reaction of Phenols (Angew. Chem. Int. Ed. 20/2014) 下载免费PDF全文
Bernd Elsler Dr. Dieter Schollmeyer Dr. Katrin Marie Dyballa Prof. Dr. Robert Franke Prof. Dr. Siegfried R. Waldvogel 《Angewandte Chemie (International ed. in English)》2014,53(20):4979-4979
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A modified synthetic route of [3,3′‐di‐sec‐butyl‐4′‐(2‐dimethylaminoethoxy)biphenyl‐4‐yloxy]acetic acid ( 1 ) with high total yield of 44% from biphenyl‐4,4′‐diol ( 2 ) is described. 相似文献
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Cover Picture: Sulfoxide‐Directed Metal‐Free ortho‐Propargylation of Aromatics and Heteroaromatics (Chem. Eur. J. 20/2015) 下载免费PDF全文
Dr. Andrew J. Eberhart Harry J. Shrives Estela Álvarez Dr. Amandine Carrër Yuntong Zhang David J. Procter 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(20):7309-7309
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Julián Bergueiro Dr. Javier Montenegro Prof. Dr. Carlos Saá Prof. Dr. Susana López 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(44):14100-14107
An expeditious, highly efficient approach to 11‐cis‐retinoids was achieved by semihydrogenation of a readily available 11‐yne precursor through a hydrosilylation–protodesilylation protocol. The complete chemo‐, regio‐, and syn‐stereoselectivity of the method also allowed direct access to 11‐ and 12‐monodeutero‐, and 11,12‐dideutero‐11‐cis‐retinoids. The analogous trans series was not accessible by this route, and was synthesized by means of Hiyama coupling. 相似文献
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Cover Picture: Source of Selectivity in Oxidative Cross‐Coupling of Aryls by Solvent Effect of 1,1,1,3,3,3‐Hexafluoropropan‐2‐ol (Chem. Eur. J. 35/2015) 下载免费PDF全文
Dr. Bernd Elsler Anton Wiebe Dr. Dieter Schollmeyer Dr. Katrin M. Dyballa Prof. Dr. Robert Franke Prof. Dr. Siegfried R. Waldvogel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(35):12205-12205
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Efficient Diketopyrrolopyrrole‐Based Small‐Molecule Bulk‐Heterojunction Solar Cells with Different Electron‐Donating End‐Groups 下载免费PDF全文
Yu Jin Kim Jang Yeol Back Seul‐Ong Kim Chan‐Woo Jeon Prof. Chan Eon Park Prof. Yun‐Hi Kim 《化学:亚洲杂志》2014,9(9):2505-2513
A series of small molecules that contained identical π‐spacers (ethyne), a central diketopyrrolopyrrole (DPP) unit, and different aromatic electron‐donating end‐groups were synthesized and used in organic solar cells (OSCs) to study the effect of electron‐donating groups on the device performance. The three compounds, DPP‐A‐Ph , DPP‐A‐Na , and DPP‐A‐An , possessed intense absorption bands that covered a wide range, from 350 to 750 nm, and relatively low HOMO energy levels, from ?5.50 to ?5.55 eV. DPP‐A‐An , which contained anthracene end‐groups, demonstrated a stronger absorbance and a higher hole mobility than DPP‐A‐Ph , which contained phenyl groups, and DPP‐A‐Na , which contained naphthalene units. The power‐conversion efficiencies (PCEs) of OSCs based on organic:PC71BM blends (1:1, w/w) with a processed DIO additive were 3.93 % for DPP‐A‐An , 3.02 % for DPP‐Na , and 2.26 % for DPP‐A‐Ph . These findings suggest that a DPP core that is functionalized with electron‐donating capping groups constitutes a promising new class of solution‐processable small molecules for OSC applications. 相似文献
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Significant Enhancement in the Efficiency and Selectivity of Iron‐Catalyzed Oxidative Cross‐Coupling of Phenols by Fluoroalcohols 下载免费PDF全文
Eden Gaster Yulia Vainer Almog Regev Dr. Sachin Narute Dr. Kavitha Sudheendran Aviya Werbeloff Hadas Shalit Dr. Doron Pappo 《Angewandte Chemie (International ed. in English)》2015,54(14):4198-4202
Significant enhancement of both the rate and the chemoselectivity of iron‐catalyzed oxidative coupling of phenols can be achieved in fluorinated solvents, such as 1,1,1,3,3,3‐hexafluoropropan‐2‐ol (HFIP), 2,2,2‐trifluoroethanol (TFE), and 1‐phenyl‐2,2,2‐trifluoroethanol. The generality of this effect was examined for the cross‐coupling of phenols with arenes and polycyclic aromatic hydrocarbons (PAHs) and of phenol with β‐dicarbonyl compounds. The new conditions were utilized in the synthesis of 2′′′‐dehydroxycalodenin B in only four synthetic steps. 相似文献
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Intramolecular Metal‐Free Oxidative Aryl–Aryl Coupling: An Unusual Hypervalent‐Iodine‐Mediated Rearrangement of 2‐Substituted N‐Phenylbenzamides 下载免费PDF全文
Siyun Shang Dr. Daisy Zhang‐Negrerie Prof. Dr. Yunfei Du Prof. Dr. Kang Zhao 《Angewandte Chemie (International ed. in English)》2014,53(24):6216-6219
Hypervalent‐iodine‐mediated oxidative coupling of the two aryl groups in either 2‐acylamino‐N‐phenyl‐benzamides or 2‐hydroxy‐N‐phenylbenzamides, with concomitant insertion of the ortho‐substituted N or O atom into the tether, has been described for the first time. This unusual metal‐free rearrangement reaction involves an oxidative C(sp2)? C(sp2) aryl–aryl bond formation, cleavage of a C(sp2)? C(O) bond, and a lactamization/lactonization. Furthermore, unsymmetrical diaryl compounds can be easily obtained by removing the tether within the cyclized product. 相似文献
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Stereospecific Pd‐Catalyzed Intermolecular C(sp3)–C(sp) Cross‐Coupling of Diarylmethyl Carbonates and Terminal Alkynes Under Base‐Free Conditions 下载免费PDF全文
Sho Tabuchi Prof. Dr. Koji Hirano Prof. Dr. Masahiro Miura 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(47):16823-16827
A palladium‐catalyzed intermolecular decarboxylative C(sp3)–C(sp) coupling of diarylmethyl carbonates and terminal alkynes has been developed. The reaction proceeds smoothly under external base‐free conditions to deliver the corresponding alkynylated diarylmethanes with the liberation of CO2 and MeOH as the sole byproducts. Moreover, enantioenriched diarylmethyl carbonates are stereospecifically converted to optically active cross‐coupling products with inversion of configuration. Thus, the stereospecific palladium catalysis can provide new and unique access to the alkynylated chiral tertiary stereocenters, which are relatively difficult to construct by conventional methods. 相似文献
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Hiyama cross‐coupling reaction catalyzed by a palladium salt of 1‐benzyl‐4‐aza‐1‐azoniabicyclo[2.2.2]octane chloride under microwave irradiation 下载免费PDF全文
An efficient catalytic system using 1‐benzyl‐4‐aza‐1‐azoniabicyclo[2.2.2]octane chloride ((BeDABCO)2Pd2Cl6) was developed for the Hiyama cross‐coupling reaction of various aryl halides with triethoxy(phenyl)silane. The substituted biaryls were produced in excellent yields in short reaction times using a catalytic amount of this catalyst in NMP at 100 °C. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
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Prof. Dr. Masaki Shimizu Yosuke Tomioka Dr. Ikuhiro Nagao Tsugumi Kadowaki Prof. Dr. Tamejiro Hiyama 《化学:亚洲杂志》2012,7(7):1644-1651
(Z)‐1,2‐Diaryl‐1,2‐bis(pinacolatoboryl)ethenes underwent double‐cross‐coupling reactions with 1‐bromo‐2‐[(Z)‐2‐bromoethenyl]arenes in the presence of [Pd(PPh3)4] as a catalyst and 3 M aqueous Cs2CO3 as a base in THF at 80 °C. The double‐coupling reaction gave multisubstituted naphthalenes in good to high yields. Annulation of 1,2‐bis(pinacolatoboryl)arenes with bromo(bromoethenyl)arenes in the presence of a catalyst system that consisted of [Pd2(dba)3] (dba=dibenzylideneacetone) and 2‐dicyclohexylphosphino‐2′,6′‐dimethoxybiphenyl (SPhos) under the same conditions produced fused phenanthrenes in good to high yields. The first annulation coupling occurred regiospecifically at the bromoethenyl moiety. This procedure is applicable to the facile synthesis of polysubstituted anthracenes, benzothiophenes, and dibenzoanthracenes through a double annulation pathway by using the corresponding dibromobis[(Z)‐2‐bromoethenyl]benzenes as diboryl coupling partners. 相似文献