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Graphical Abstract Angew. Chem. Int. Ed. 32006

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The following Communications have been judged by at least two referees to be ?very
important papers? and will be published online at soon:
J. Deschamp, O. Chuzel, J. Hannedouche, O. Riant*
Highly Diastereo- and Enantioselective Copper-Catalyzed
Tandem Conjugated Reduction/Aldol Reaction to Ketones
J. W. Bode,* R. M. Fox, K. D. Baucom
Chemoselective Amide Ligations by Decarboxylative
Condensations of N-Alkylhydroxylamines and a-Keto Acids
A. Oleksi, A. G. Blanco, R. Boer, I. Us*n, J. Aymam,, A. Rodger,
M. J. Hannon,* M. Coll*
Molecular Recognition of a Three-Way DNA Junction by a
Metallosupramolecular Helicate
J. E. Banham, C. R. Timmel, R. J. M. Abbott, S. M. Lea,*
G. Jeschke*
Characterization of Weak Protein?Protein Interactions: Evidence
from DEER for the Trimerization of a von Willebrand Factor A
Domain in Solution
B. H. Lipshutz,* B. A. Frieman, A. E. Tomaso, Jr.
Copper-in-Charcoal (Cu/C): Heterogeneous, Copper-Catalyzed
Asymmetric Hydrosilylations
J. T. Shaw,* J. M. Mitchell
A Structurally Diverse Library of Polycyclic Lactams Resulting
from the Systematic Placement of Proximal Functional Groups
Meeting Reviews
Chembiogenesis 2005 and Systems Chemistry Workshop
J. Stankiewicz, L. H. Eckardt
P. Skrabal
Heinrich Zollinger (1919?2005): Renovator of Dyestuff and Textile Chemistry
Silicon-Mediated Transformations of
Functional Groups
Helmut Vorbr-ggen
reviewed by T. Mller, N. Auner
Charge Transfer in DNA
Hans-Achim Wagenknecht
reviewed by T. von Feilitzsch
A wide variety of optically active compounds as well as active compounds such
as amino acid derivatives can be accessed
by the cross-Mannich reaction of aldehydes, particularly by the direct catalytic
asymmetric version, in which CC bonds
are formed. Remarkable advancements
have been reported, including one-pot,
three-component procedures with absolute stereocontrol and high yields (see
example, NMP = N-methylpyrrolidine).
Asymmetric Catalysis
M. M. B. Marques*
348 ? 352
Catalytic Enantioselective Cross-Mannich
Reaction of Aldehydes
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2006, 45, 330 ? 340
Tandem Transformations
H.-C. Guo, J.-A. Ma*
354 ? 366
Catalytic Asymmetric Tandem
Transformations Triggered by Conjugate
Conjugate additions lead the way in
catalytic asymmetric tandem transformations, which allow rapid access to complex
molecular structures from readily available starting compounds. The advantage
of such transformations is the formation
of several bonds and the creation of two or
more contiguous stereogenic centers by
using a single catalyst in one pot (see
Superheavy Elements
368 ? 401
M. Sch:del*
Chemistry of Superheavy Elements
Man-made atoms: Experimental techniques, such as hot fusion (see scheme)
and theoretical calculations on the superheavy elements (the transactinides) are
now shedding light on the chemistry of
these elements. Nuclear chemistry, performed at the ultimate one-atom-at-a-time
limit, has reached element 108, hassium,
and the elements 112 and beyond are now
under investigation.
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Angew. Chem. Int. Ed. 2006, 45, 330 ? 340
Structural changes that occur at the
palladium(111)/water interface during the
electrocatalytic oxidation and reduction of
water (see picture) have been calculated
by ab initio methods. These results have
been used to construct an electrochemical
phase diagram, and demonstrate the
influence of the polarization of the water/
metal interface on surface properties.
postage paid at Jamaica NY 11431. US POSTMASTER: send address changes to Angewandte
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J.-S. Filhol, M. Neurock*
402 ? 406
Elucidation of the Electrochemical
Activation of Water over Pd by First
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Bond formation between single Pt atoms
and surface thiol groups is the result of
the reduction of a Pt precursor in the
presence of surface-thiolated carbon
nanotubes. By setting the temperature of
the following heat treatment, finely sizecontrolled and monodispersed Pt clusters
were obtained from the dispersed single
atoms (see picture).
The probable reaction pathways for propylene epoxidation with O2 and H2 in the
presence of trimethylamine on trimethylsilylated Au-Ba(NO3)2/titanosilicate catalyst are discussed (see figure). The use of
trimethylamine as a gas-phase promoter
for nanoparticulate gold catalysts leads to
a direct one-stage production of propylene
oxide (PO) with steady space?time yields
comparable to values for current industrial ethylene oxide production.
Y.-T. Kim, K. Ohshima, K. Higashimine,
T. Uruga, M. Takata, H. Suematsu,
T. Mitani*
407 ? 411
Fine Size Control of Platinum on Carbon
Nanotubes: From Single Atoms to
Epoxidation Catalysts
B. Chowdhury, J. J. Bravo-SuIrez, M. DatJ,
S. Tsubota, M. Haruta*
412 ? 415
Trimethylamine as a Gas-Phase Promoter:
Highly Efficient Epoxidation of Propylene
over Supported Gold Catalysts
Proton Transfer
Proton relay in cyclic 7-hydroxyquinoline?
(alcohol)2 complexes (see picture) has
been explored in nonpolar solvents. The
asymmetric triple proton transfer has an
unusually large, temperature-independent, and viscosity-dependent kinetic isotope effect. Heavy-atom motions (wavy
arrow) of solvent and bridging molecules
allow proton tunneling by assisting the
complex to reach the optimal precursor
O.-H. Kwon, Y.-S. Lee, B. K. Yoo,
D.-J. Jang*
415 ? 419
Excited-State Triple Proton Transfer of
7-Hydroxyquinoline along a HydrogenBonded Alcohol Chain: Vibrationally
Assisted Proton Tunneling
Bring in the substitute! Zn1xCoxO nanowires are prepared by using a solutionbased synthetic route. Structural, optical,
and spectroscopic characterizations indicate that the cobalt atoms substitute the
zinc cations in the host lattice as a result
of the cobalt doping (the picture shows
prepared Co-doped ZnO nanowires).
Angew. Chem. Int. Ed. 2006, 45, 330 ? 340
Electrocatalyst Design
B. D. Yuhas, D. O. Zitoun,
P. J. Pauzauskie, R. He,
P. Yang*
420 ? 423
Transition-Metal-Doped Zinc Oxide
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Total Synthesis
M. Rodriquez, S. Terracciano, E. Cini,
G. Settembrini, I. Bruno, G. Bifulco,
M. Taddei,*
L. Gomez-Paloma*
423 ? 427
Total Synthesis, NMR Solution Structure,
and Binding Model of the Potent Histone
Deacetylase Inhibitor FR235222
An alternative route: The fungal metabolite FR235222, a potent inhibitor of mammalian histone deacetylase (HDAC), has
been synthesized. Key steps are the preparation of unusual amino acids Ahoda
and (2R,4S)-MePro. A 3D model for
cyclopeptide inhibitor interaction with the
HDAC active site (see picture) highlights
the differences between the binding mode
of small-molecule and cyclopeptide inhibitors.
Materials Science
Speed up: In situ formation of perovskite
phases (CadTiOx, x/d 2) during electroreduction of porous TiO2 pellets to Ti
metal in molten CaCl2 kinetically retards
the process. Ex situ perovskitization of
TiO2 with CaO (see picture) can prevent in
situ perovskitization during electrolysis,
thereby significantly increasing the electroreduction speed.
K. Jiang, X. H. Hu, M. Ma, D. H. Wang,*
G. H. Qiu, X. B. Jin,
G. Z. Chen*
428 ? 432
Electrochemical Reduction of Solid TiO2
in Molten CaCl2
Cluster Compounds
A. K. Boudalis,* C. P. Raptopoulou,
B. Abarca, R. Ballesteros, M. Chadlaoui,
J.-P. Tuchagues, A. Terzis
432 ? 435
CoII Chemistry of 2,6-Bis(2pyridylcarbonyl)pyridine: An Icosanuclear
Co Cluster Exhibiting Superparamagnetic
Giant clusters: Metal-assisted hydrolysis
of 2,6-bis(2-pyridylcarbonyl)pyridine with
Co(O2CMe)2и4 H2O in hot DMF yielded an
icosanuclear CoII complex containing the
triply deprotonated bis(gem-diol) form of
the ligand and exhibiting superparamagnetic relaxation of its magnetization. The
picture shows the central Co?O core of
the complex (Co violet, O red).
Electrostatic Interactions
G. MQnguez Espallargas, L. Brammer,*
P. Sherwood
435 ? 440
Designing Intermolecular Interactions
between Halogenated Peripheries of
Inorganic and Organic Molecules:
Electrostatically Directed MXиииX?C
Halogen Bonds
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Complementary electronic properties of
inorganic and organic halogen species are
exploited in the design of molecular networks that employ MXиииX?C halogen
bonds. The dominance of electrostatic
effects in this type of interaction over
other energy terms, such as charge
transfer, is demonstrated by the study of a
series of eight isostructural compounds
(4-X?pyH)2[CoX4] (see picture; X = Cl, Cl/
Br, Br, I; X? = Cl, Br).
Angew. Chem. Int. Ed. 2006, 45, 330 ? 340
The additional molecule of methyllithium
present in [(Me4Fe)(MeLi)][Li(OEt2)]2 (1),
the first structurally characterized ate
complex of FeII bearing only alkyl substituents without any further stabilizing
ligands (see picture: Fe: magenta; Li:
cyan; O: red; C and H: gray), is a
particularly remarkable structural feature
and contributes to the fascinating reactivity profile of 1 in the title reactions.
Synthetic Methods
Hot air in a hurry: An industrial Fe-Mo-O
catalyst, used in the production of formaldehyde has been studied under redox
conditions using rapid in situ powder
diffraction studies (see contour image).
Surprisingly, the oxidation step is fastest
as it is completed within 15 s at 472 8C.
Oxidation Reactions
A. F-rstner,* H. Krause,
C. W. Lehmann
Unusual Structure and Reactivity of a
Homoleptic ?Super-Ate? Complex of Iron:
Implications for Grignard Additions,
Cross-Coupling Reactions, and the
Kharasch Deconjugation
S. D. M. Jacques, O. Leynaud,
D. Strusevich, A. M. Beale, G. Sankar,
C. M. Martin, P. Barnes*
445 ? 448
Redox Behavior of Fe-Mo-O Catalysts
Studied by Ultrarapid In Situ Diffraction
Remarkable selectivity (88 % in the
steady-state reaction and 94 % in the
pulse reaction) is observed in the direct
synthesis of phenol from benzene with
molecular oxygen over a Re/zeolite catalyst prepared by chemical-vapor deposition. The novel interstitial-N/Re clusters
are formed with NH3 and are essential for
the activity in the selective oxidation
Hidden qualities: [Rh(PiPr3)(C14H16)][BArF4] (1; see picture of the cation;
P violet, Rh olive green), which was synthesized by treatment of [RhCl(nbd)(PiPr3)] with Na[BArF4] (BArF4 = B{C6H3(CF3)2}4) and norbornadiene (nbd) in
fluorobenzene, contains an organic fragment derived from Binor-S as well as
agostic RhиииCC and RhиииHC interactions.
In solution, 1 undergoes rapid, reversible
CC activation/reductive elimination.
Angew. Chem. Int. Ed. 2006, 45, 330 ? 340
440 ? 444
Phenol Synthesis
R. Bal, M. Tada, T. Sasaki,
Y. Iwasawa*
448 ? 452
Direct Phenol Synthesis by Selective
Oxidation of Benzene with Molecular
Oxygen on an Interstitial-N/Re Cluster/
Zeolite Catalyst
CC Activation
S. K. Brayshaw, J. C. Green,
G. Kociok-KUhn, E. L. Sceats,
A. S. Weller*
452 ? 456
A Rhodium Complex with One RhиииCC
and One RhиииHC Agostic Bond
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Helical Structures
Good cholesterol: Oligo(p-phenylenevinylene)s (OPVs) that are mono- or disubstituted with cholesterol moieties
form pseudo-J and pseudo-H aggregates,
respectively (see picture), which lead to
coiled and twisted helical structures with
distinct optical, chiroptical, and morphological properties.
A. Ajayaghosh,* C. Vijayakumar,
R. Varghese, S. J. George
456 ? 460
Cholesterol-Aided Supramolecular
Control over Chromophore Packing:
Twisted and Coiled Helices with Distinct
Optical, Chiroptical, and Morphological
Supramolecular Chemistry
Artificial cells: A polyoxomolybdate capsule, in which the cavity is linked to
surface pores by channels, can take up
Pr3+ ions. Each uptake reduces the negative charge on the capsule so that eventually no more Pr3+ ions enter the capsule,
instead they remain bound on the surface
(see structure: external hydrated
Pr3+ green polyhedra, encapsulated
Pr3+ light green, Mo blue, O red,
SO42 yellow). This process models voltage gating of the ion channels of cells.
A. M-ller,* Y. Zhou, H. BUgge,
M. Schmidtmann, T. Mitra, E. T. K. Haupt,
A. Berkle
460 ? 465
?Gating? the Pores of a Metal Oxide
Based Capsule: After Initial Cation Uptake
Subsequent Cations Are Found Hydrated
and Supramolecularly Fixed above the
Organometallic Chemistry
N. Chinkov, A. Levin,
I. Marek*
465 ? 468
Unsaturated Fatty Alcohol Derivatives as a
Source of Substituted Allylzirconocene
From A to Z: Allylzirconocenes have been
easily prepared in a one-pot procedure
through a tandem allylic CH activation?
b-elimination reaction from unsaturated
fatty alcohol and ether starting materials
(see scheme). The reaction proceeds
rapidly under mild condition and is
insensitive to the length of the carbon
tether between the double bond and the
alcohol moiety.
Protection strategy: Glycosylphosphatidylinositols (GPIs) from the Trypanosoma
cruzi parasite (a causative agent of
Chagas? disease) that contain an unsaturated fatty acid in the lipid moiety (see
partial structure of 1, R = (CH2)7CH=CH-
(CH2)7CH3, and 2, R = (CH2)7CH=
CHCH2CH=CH(CH2)4CH3) were prepared
by a strategy that employs non-benzyl-type
protecting groups. The synthetic GPIs
show similar biological activity to their
natural counterparts.
Synthetic Methods
D. V. Yashunsky, V. S. Borodkin,
M. A. J. Ferguson,
A. V. Nikolaev*
468 ? 474
The Chemical Synthesis of Bioactive
Glycosylphosphatidylinositols from
Trypanosoma cruzi Containing an
Unsaturated Fatty Acid in the Lipid
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2006, 45, 330 ? 340
A new synthesis of iridabenzene species
involves the coupling of MeCH=CH2 with
iridacycles 1 and 2. Surprisingly, the
structure of the coupling product of the
iridacyclopentadienes with propene (3 or
4) is highly susceptible to the nature of the
substituents in the starting metallacycle.
E. Zlvarez, M. Paneque,* M. L. Poveda,*
N. Rend[n
474 ? 477
Formation of Iridabenzenes by Coupling
of Iridacyclopentadienes and Alkenes
Peptide Synthesis
J. M. Palomo, M. Lumbierres,
H. Waldmann*
Anchored down: Long lipopeptides (up to
26 amino acids) that carry multiple sensitive lipid residues as well as different
reporter groups and tags can be synthe-
sized efficiently by employing the Ellman
sulfonamide linker as an anchoring group
to the solid support (SPPS = solid-phase
peptide synthesis).
477 ? 481
Efficient Solid-Phase Lipopeptide
Synthesis Employing the Ellman
Sulfonamide Linker
Synthetic Methods
T. Mitsudome, T. Umetani, N. Nosaka,
K. Mori, T. Mizugaki, K. Ebitani,
K. Kaneda*
481 ? 485
Just the one: The combination of palladium dichloride and N,N-dimethylacetamide (DMA) constitutes a highly efficient
and reusable catalytic system, which uses
molecular oxygen as the sole reoxidant for
liquid-phase Wacker oxidation and acetoxylation of terminal olefins to the corresponding methyl ketones and linear allylic
acetates, respectively (see scheme).
Convenient and Efficient Pd-Catalyzed
Regioselective Oxyfunctionalization of
Terminal Olefins by Using Molecular
Oxygen as Sole Reoxidant
Cleavage Reactions
T. Kawashima, T. Takao,
H. Suzuki*
Broken bonds: The reaction of [(Cp*Ru)3(m-H)3(m3-H)2] (1, Cp* = h5-C5Me5) with an
equimolar amount of benzonitrile yields
the m3-nitrido-m3-allyl complex 2 as a result
Angew. Chem. Int. Ed. 2006, 45, 330 ? 340
of the CN bond cleavage (see scheme).
The CN bond cleavage proceeds through
the formation of m3(?)-iminoacyl complex
[(Cp*Ru)3(m3-h2 :h2(? )-PhCNH)(m-H)2].
485 ? 488
Cleavage of the CN Bond on a
Triruthenium Cluster: Synthesis and
Structure of a Triruthenium Complex
Containing a m3-Nitrido Ligand
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Synthesis Design
I. A. I. Mkhalid, D. N. Coventry,
D. Albesa-Jove, A. S. Batsanov,
J. A. K. Howard, R. N. Perutz,
T. B. Marder*
489 ? 491
Ir-Catalyzed Borylation of CH Bonds in
N-Containing Heterocycles:
Regioselectivity in the Synthesis of
Heteroaryl Boronate Esters
Blocking the way: Substitution at the 2position in pyridines and other N-heterocycles blocks N-coordination to an Ir
center. This steric hindrance provides a
substrate-design criterion that allows the
Ir-catalyzed borylation of CH bonds,
which can be followed by Suzuki?Miyaura
cross-coupling in a one-pot reaction (see
scheme; B2pin2 = bis(pinacolato-O,O?)diboron, dtbpy = 4,4?-tBu2-2,2?-bipyridine).
The famous five: The elusive five-coordinate nitrito complexes [FeIII(por)(ONO)]
(por = meso-tetraphenylporphyrinato dianion or meso-tetra-p-tolylporphyrinato dianion) have been obtained by interaction
of low-pressure NO2 with sublimed layers
of [FeII(por)]. Spectral data confirm that
the NO2 ligand prefers to bind through O
coordination but adopts the N-bonded
configuration when the second axial site is
occupied (R = Ph, p-tolyl).
Easy-to-prepare solutions of LnCl3и2 LiCl
(Ln = La, Ce, Nd) (0.3?0.5 m in THF) are a
unique source of soluble lanthanide salts
with versatile applications in organic
synthesis. These salts can serve as pro-
moters or catalysts for the addition of
organometallic compounds to sterically
hindered, enolizable or a,b-unsaturated
ketones or imines.
Predictable ion selectivity is a major goal
for the use of synthetic channels in
biological systems. Gramicidin A (gA) is a
suitable lead structure for the design of
such channels. The crown ether?gA hybrid
structure shown forms ion channels with
a higher ion selectivity for K+ than for Cs+.
Porphyrin Complexes
T. S. Kurtikyan,* P. C. Ford*
492 ? 496
Reactions of Nitrogen Oxides with Heme
Models: Spectral Characterization of an
Elusive Five-Coordinate FeIII(porphyrin)
Nitrito Intermediate
Grignard Reactions
A. Krasovskiy, F. Kopp,
P. Knochel*
497 ? 500
Soluble Lanthanide Salts (LnCl3и2 LiCl) for
the Improved Addition of
Organomagnesium Reagents to Carbonyl
Ion Channels
J. R. Pfeifer, P. Rei▀, U. Koert*
501 ? 504
Crown Ether?Gramicidin Hybrid Ion
Channels: Dehydration-Assisted Ion
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2006, 45, 330 ? 340
Synthesis with light: CdS quantum dots
(QDs) generate superoxide and hydroxyl
radicals upon UV irradiation in aqueous
solution. The radicals are used for activating P450BSb enzymes attached at the
QD surface, effecting the catalytic transformation of myristic acid into a- and bhydroxymyristic acid (see picture,
R = (CH2)10CH3).
B. I. Ipe, C. M. Niemeyer*
504 ? 507
Nanohybrids Composed of Quantum
Dots and Cytochrome P450 as
Fluorescent Probes
O. Wichmann, J. Wittbrodt,
C. Schultz*
Watching live: The FRET reporter PENN/
SATE (see picture; FRET = fluorescence
resonance energy transfer) is membrane
permeant and enters cells and small
organisms by using a prodrug approach.
Once inside cells the reporter is cleaved by
phospholipases, which results in a 30-fold
change in the emission ratio
508 ? 512
A Small-Molecule FRET Probe To Monitor
Phospholipase A2 Activity in Cells and
Angewandte?s Sister Journals 516 ? 517
Angew. Chem. Int. Ed. 2006, 45, 330 ? 340
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Aqueous FeIV=O: Spectroscopic
Identification and Oxo-Group Exchange
O. Pestovsky, S. Stoian, E. L. Bominaar,
X. Shan, E. M-nck,* L. Que, Jr.,*
A. Bakac*
In Figure 1, the MUssbauer spectrum measured at 8.0 T was inadvertently also shown as
that measured at 4.0 T. The revised Figure 1 shown herein contains the correct
spectrum obtained at 4.0 T. The authors apologize for this oversight and would like to
emphasize that the error has no bearing on any parameter reported in the manuscript
and does not affect the discussion of the results.
Angew. Chem. Int. Ed. 2005, 44
DOI 10.1002/anie.200502686
Figure 1. MUssbauer spectra of a sample at 4.2 K containing 250 mm Z, prepared by the rapid
freeze?quench technique (see Supporting Information). The solid lines (red for Z, representing
ca. 50 % of total Fe) are simulations based on Equation (2). The contribution from [Fe(H2O)6]3+ is
shown in blue. We found the following parameters for Z: D = 9.7(7) cm1, Ax/gn bn = Ay/
gn bn = 20.3(3) T, DEQ = 0.33(3) mm s1, d = 0.38(2) mm s1. For the 8.0-T spectrum, the
theoretical curves for Z and [Fe(H2O)6]3+ were added (black).
In addition, the authors would like to acknowledge the Stanford Synchrotron Radiation
Laboratory (SSRL), a national user facility operated by Stanford University on behalf of
the US Department of Energy, for the X-ray absorption measurements. The SSRL
Structural Molecular Biology Program is supported by the Department of Energy, Office
of Biological Environmental Research, and by the NIH, National Center for Research
Resources, Biomedical Technology Program.
Organocatalytic Asymmetric
a-Halogenation of 1,3-Dicarbonyl
In this Communication, the structure of methyl-2-oxo-1-indanecarboxylate (1 d) was
rendered incorrectly; the correct structure is shown. The authors apologize for this
G. Bartoli,* M. Basco, A. Carlone,
M. Locatelli, P. Melchiorre,*
L. Sambri
Angew. Chem. Int. Ed. 2005, 44
DOI 10.1002/anie.200502134
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2006, 45, 330 ? 340
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