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951.
Iridium(I)‐Catalyzed Regioselective CH Activation and Hydrogen‐Isotope Exchange of Non‐aromatic Unsaturated Functionality
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Prof. Dr. William J. Kerr Richard J. Mudd Dr. Laura C. Paterson Dr. Jack A. Brown 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(45):14604-14607
Isotopic labelling is a key technology of increasing importance for the investigation of new C?H activation and functionalization techniques, as well as in the construction of labelled molecules for use within both organic synthesis and drug discovery. Herein, we report for the first time selective iridium‐catalyzed C?H activation and hydrogen‐isotope exchange at the β‐position of unsaturated organic compounds. The use of our highly active [Ir(cod)(IMes)(PPh3)][PF6] (cod=1,5‐cyclooctadiene) catalyst, under mild reaction conditions, allows the regioselective β‐activation and labelling of a range of α,β‐unsaturated compounds with differing steric and electronic properties. This new process delivers high levels of isotope incorporation over short reaction times by using low levels of catalyst loading. 相似文献
952.
Regiospecific Formation and Unusual Optical Properties of 2,5‐Bis(arylethynyl)rhodacyclopentadienes: A New Class of Luminescent Organometallics
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Dr. Andreas Steffen Dr. Richard M. Ward Dr. Meng Guan Tay Dr. Robert M. Edkins Dr. Fabian Seeler Magda van Leeuwen Dr. Lars‐Olof Pålsson Prof. Dr. Andrew Beeby Dr. Andrei S. Batsanov Prof. Dr. Judith A. K. Howard Prof. Dr. Todd B. Marder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(13):3652-3666
A series of 2,5‐bis(arylethynyl)rhodacyclopentadienes has been prepared by a rare example of regiospecific reductive coupling of 1,4‐(p‐R‐phenyl)‐1,3‐butadiynes (R?H, Me, OMe, SMe, NMe2, CF3, CO2Me, CN, NO2, ?C?C‐(p‐C6H4?NHex2), ?C?C?(p‐C6H4?CO2Oct)) at [RhX(PMe3)4] ( 1 ) (X=?C?C?SiMe3 ( a ), ?C?C‐(p‐C6H4?NMe2) ( b ), ?C?C?C?C?(p‐C6H4?NPh2) ( c ) or ?C?C?{p‐C6H4‐C?C?(p‐C6H4‐N(C6H13)2)} ( d ) or Me ( e )), giving the 2,5‐bis(arylethynyl) isomer exclusively. The rhodacyclopentadienes bearing a methyl ligand in the equatorial plane (compound 1 e ) have been converted into their chloro analogues by reaction with HCl etherate. The rhodacycles thus obtained are stable to air and moisture in the solid state and the acceptor‐substituted compounds are even stable to air and moisture in solution. The photophysical properties of the rhodacyclopentadienes are highly unusual in that they exhibit, exclusively, fluorescence between 500–800 nm from the S1 state, with quantum yields of Φ=0.01–0.18 and short lifetimes (τ=0.45–8.20 ns). The triplet state formation (ΦISC=0.57 for 2 a ) is exceptionally slow, occurring on the nanosecond timescale. This is unexpected, because the Rh atom should normally facilitate intersystem crossing within femto‐ to picoseconds, leading to phosphorescence from the T1 state. This work therefore highlights that in some transition‐metal complexes, the heavy atom can play a more subtle role in controlling the photophysical behavior than is commonly appreciated. 相似文献
953.
Phenylalanine Ammonia Lyase Catalyzed Synthesis of Amino Acids by an MIO‐Cofactor Independent Pathway
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Sarah L. Lovelock Dr. Richard C. Lloyd Prof. Nicholas J. Turner 《Angewandte Chemie (International ed. in English)》2014,53(18):4652-4656
Phenylalanine ammonia lyases (PALs) belong to a family of 4‐methylideneimidazole‐5‐one (MIO) cofactor dependent enzymes which are responsible for the conversion of L ‐phenylalanine into trans‐cinnamic acid in eukaryotic and prokaryotic organisms. Under conditions of high ammonia concentration, this deamination reaction is reversible and hence there is considerable interest in the development of PALs as biocatalysts for the enantioselective synthesis of non‐natural amino acids. Herein the discovery of a previously unobserved competing MIO‐independent reaction pathway, which proceeds in a non‐stereoselective manner and results in the generation of both L ‐ and D ‐phenylalanine derivatives, is described. The mechanism of the MIO‐independent pathway is explored through isotopic‐labeling studies and mutagenesis of key active‐site residues. The results obtained are consistent with amino acid deamination occurring by a stepwise E1cB elimination mechanism. 相似文献
954.
Léna Sambe Victor R. de La Rosa Khaled Belal Dr. François Stoffelbach Dr. Joel Lyskawa Dr. François Delattre Marc Bria Prof. Graeme Cooke Prof. Richard Hoogenboom Prof. Patrice Woisel 《Angewandte Chemie (International ed. in English)》2014,53(20):5044-5048
A new class of polymeric thermometers with a memory function is reported that is based on the supramolecular host–guest interactions of poly(N‐isopropylacrylamide) (PNIPAM) with side‐chain naphthalene guest moieties and the tetracationic macrocycle cyclobis(paraquat‐p‐phenylene) (CBPQT4+) as the host. This supramolecular thermometer exhibits a memory function for the thermal history of the solution, which arises from the large hysteresis of the thermoresponsive LCST phase transition (LCST=lower critical solution temperature). This hysteresis is based on the formation of a metastable soluble state that consists of the PNIPAM–CBPQT4+ host–guest complex. When heated above the transition temperature, the polymer collapses, and the host–guest interactions are disrupted, making the polymer more hydrophobic and less soluble in water. Aside from providing fundamental insights into the kinetic control of supramolecular assemblies, the developed thermometer with a memory function might find use in applications spanning the physical and biological sciences. 相似文献
955.
Prof. Li Chen Genevieve E. Mullen Myriam Le Roch Cody G. Cassity Prof. Nicolas Gouault Prof. Henry Y. Fadamiro Prof. Robert E. Barletta Prof. Richard A. O'Brien Prof. Richard E. Sykora Prof. Alexandra C. Stenson Prof. Kevin N. West Howard E. Horne Jeffrey M. Hendrich Kang Rui Xiang Prof. James H. Davis Jr. 《Angewandte Chemie (International ed. in English)》2014,53(44):11762-11765
The practical utility of ionic liquids (ILs) makes the absence (heretofore) of reported examples from nature quite puzzling, given the facility with which nature produces many other types of exotic but utilitarian substances. In that vein, we report here the identification and characterization of a naturally occurring protic IL. It can be formed during confrontations between the ants S. invicta and N. fulva. After being sprayed with alkaloid‐based S. invicta venom, N. fulva detoxifies by grooming with its own venom, formic acid. The mixture is a viscous liquid manifestly different from either of the constituents. Further, we find that the change results as a consequence of formic acid protonation of the N centers of the S. invicta venom alkaloids. The resulting mixed‐cation ammonium formate milieu has properties consistent with its classification as a protic IL. 相似文献
956.
A Supramolecular Sorting Hat: Stereocontrol in Metal–Ligand Self‐Assembly by Complementary Hydrogen Bonding
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Michael C. Young Lauren R. Holloway Amber M. Johnson Prof. Richard J. Hooley 《Angewandte Chemie (International ed. in English)》2014,53(37):9832-9836
A combination of self‐complementary hydrogen bonding and metal–ligand interactions allows stereocontrol in the self‐assembly of prochiral ligand scaffolds. A unique, non‐tetrahedral M4L6 structure is observed upon multicomponent self‐assembly of 2,7‐diaminofluorenol with 2‐formylpyridine and Fe(ClO4)2. The stereochemical outcome of the assembly is controlled by self‐complementary hydrogen bonding between both individual ligands and a suitably sized counterion as template. This hydrogen‐bonding‐mediated stereoselective metal–ligand assembly allows the controlled formation of nonsymmetric discrete cage structures from previously unexploited ligand scaffolds. 相似文献
957.
Dr. Elena Madrid Yuanyang Rong Dr. Mariolino Carta Prof. Neil B. McKeown Richard Malpass‐Evans Prof. Gary A. Attard Tomos J. Clarke Prof. Stuart H. Taylor Prof. Yi‐Tao Long Prof. Frank Marken 《Angewandte Chemie (International ed. in English)》2014,53(40):10751-10754
A highly rigid amine‐based polymer of intrinsic microporosity (PIM), prepared by a polymerization reaction involving the formation of Tröger’s base, is demonstrated to act as an ionic diode with electrolyte‐dependent bistable switchable states. 相似文献
958.
Dr. Richard D. Adams Dr. Vitaly Rassolov Yuen Onn Wong 《Angewandte Chemie (International ed. in English)》2014,53(41):11006-11009
The electronically unsaturated dirhenium complex [Re2(CO)8(µ‐AuPPh3)(µ‐Ph)] ( 1 ) was obtained from the reaction of [Re2(CO)8{µ‐η2‐C(H)?C(H)nBu}(µ‐H)] with [Au(PPh3)Ph]. The bridging {AuPPh3} group was replaced by a bridging hydrido ligand to yield the unsaturated dirhenium complex [Re2(CO)8(µ‐H)(µ‐Ph)] ( 2 ) by reaction of 1 with HSnPh3. Compound 2 reductively eliminates benzene upon addition of NCMe at 25 °C. The electronic structure of 2 and the mechanism of the reductive elimination of the benzene molecule in its reaction with NCMe were investigated by DFT computational analyses. 相似文献
959.
Dr. Cheng‐Chung Lee Dr. Manuel Maestre‐Reyna Dr. Kai‐Cheng Hsu Prof. Dr. Hao‐Ching Wang Prof. Dr. Chia‐I Liu Prof. Dr. Wen‐Yih Jeng Li‐Ling Lin Richard Wood Dr. Chia‐Cheng Chou Prof. Dr. Jinn‐Moon Yang Prof. Dr. Andrew H.‐J. Wang 《Angewandte Chemie (International ed. in English)》2014,53(48):13054-13058
Crown ethers are small, cyclic polyethers that have found wide‐spread use in phase‐transfer catalysis and, to a certain degree, in protein chemistry. Crown ethers readily bind metallic and organic cations, including positively charged amino acid side chains. We elucidated the crystal structures of several protein‐crown ether co‐crystals grown in the presence of 18‐crown‐6. We then employed biophysical methods and molecular dynamics simulations to compare these complexes with the corresponding apoproteins and with similar complexes with ring‐shaped low‐molecular‐weight polyethylene glycols. Our studies show that crown ethers can modify protein surface behavior dramatically by stabilizing either intra‐ or intermolecular interactions. Consequently, we propose that crown ethers can be used to modulate a wide variety of protein surface behaviors, such as oligomerization, domain–domain interactions, stabilization in organic solvents, and crystallization. 相似文献
960.
Inside Back Cover: Molecular Salt Effects in the Gas Phase: Tuning the Kinetic Basicity of [HCCLiCl]− and [HCCMgCl2]− by LiCl and MgCl2 (Angew. Chem. Int. Ed. 41/2014)
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