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Graphical Abstract Angew. Chem. Int. Ed. 312005

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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:
A. C. Filippou,* G. Schnakenburg, A. I. Philippopoulos,
N. Weidemann
Bonding Analysis of the MGeGeM Chain in the Germylidyne
Complexes trans,trans-[Cl(depe)2MGeGeM(depe)2Cl]
M. Veith*
Cubane-Type Li4H4 and Li3H3Li(OH): Stabilized in Molecular
Adducts with Alane
S. Protti, M. Fagnoni,* A. Albini*
Photochemical Cross-Coupling Reactions of Electron-Rich Aryl
Chlorides and Aryl Esters with Alkynes: A Metal-Free Alkynylation
V. Lavallo, Y. Canac, C. Pr'sang, B. Donnadieu, G. Bertrand*
Stable Cyclic (Alkyl)(amino)carbenes as Rigid or Flexible, Bulky,
Electron-Rich Ligands for Transition-Metal Catalysts
H. Braunschweig,* K. Radacki, D. Rais, D. Scheschkewitz
A T-Shaped Platinum(II) Boryl Complex as the Precursor to a
Base-Stabilized Borylene of Platinum
S. Aime,* D. D. Castelli, E. Terreno
Highly Sensitive MRI-CEST Agents using Liposomes (LIPOCEST)
Meeting Reviews
S. J. Rowan*
4830 ? 4832
Edmund Buerlein
reviewed by S. Weiner
The Merck Druggernaut
Fran Hawthorne
reviewed by A. Kleemann
Actinides in action: The structural
chemistry of the second-row f metals has
received much attention over the past
decade. Recently reported actinide-based
nanotubules and nanospheres (see picture) offer prospective materials for ion
transport and storage or as catalysts.
Actinide Nanostructures
T. E. Albrecht-Schmitt*
4836 ? 4838
Actinide Materials Adopt Curvature:
Nanotubules and Nanospheres
Semiconductor Nanocrystals
A. Eychm'ller*
4839 ? 4841
Aerogels from Semiconductor
The door to a new class of materials has
been opened through the combination of
aerogels and semiconductor nanocrys-
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
tals. Semiconductor nanoparticles are
used as building blocks to give dry,
mesoporous aerogels with large internal
surface areas (see picture, center: wet CdS
gel; left: unwashed CdS aerogel; right:
monolithic CdS aerogel; scale in mm).
These materials have many potential uses
including in photovoltaic devices and
Angew. Chem. Int. Ed. 2005, 44, 4818 ? 4827
Host?Guest Systems
Is there anything cucurbituril can?t do?
With the cucurbit[n]uril family (see spacefilling models of some examples) growing
to include homologues, derivatives, congeners, and analogues, the tentative
answer looks to be ?No?. The aim of the
Review is to convince the reader of this
optimistic assessment.
J. Lagona, P. Mukhopadhyay,
S. Chakrabarti, L. Isaacs*
4844 ? 4870
The Cucurbit[n]uril Family
Thermochromic Polymers
A brush with success: Responsive brushes composed of poly(N-isopropylacrylamide) grafted onto a poly(thiophene) backbone display the highest
water solubility ever reported for a neutral
poly(thiophene) as well as temperaturedependent optical properties and water
solubilities (see picture). The graft polymer exhibits shifts in the p?p* transition
of the poly(thiophene) backbone near the
collapse temperature of the poly(N-isopropylacrylamide) chains.
S. S. Balamurugan, G. B. Bantchev,
Y. Yang, R. L. McCarley*
4872 ? 4876
Highly Water-Soluble Thermally
Responsive Poly(thiophene)-Based
Asymmetric Catalysis
H. Sund7n, I. Ibrahem, L. Eriksson,
A. C8rdova*
4877 ? 4880
Proline and its derivatives catalyze the
asymmetric one-pot three-component
aza-Diels?Alder reaction between unmodified a,b-unsaturated cyclic ketones,
aqueous formaldehyde, and aryl amines
with excellent chemo- and enantioselectivities (see scheme). Furthermore, this
reaction provides a highly enantioselective entry to bicyclic non-proteogenic
amino acid derivatives.
Direct Catalytic Enantioselective
Aza-Diels?Alder Reactions
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Angew. Chem. Int. Ed. 2005, 44, 4818 ? 4827
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Energy Transfer
M. W. Cooke, G. S. Hanan,* F. Loiseau,
S. Campagna,* M. Watanabe,
Y. Tanaka*
4881 ? 4884
The Structural and Functional Roles of
Rhodium(ii)?Rhodium(ii) Dimers in
Multinuclear Ruthenium(ii) Complexes
Giving in to templation: Coordination of
acid-functionalized {Ru(tpy)2}2+ units
(tpy = 2,2?:6?,2??-terpyridine) to a tetracarboxylato rhodium dimer leads to multinuclear polypyridylruthenium(ii) complexes (see crystal structure, orange: Ru,
purple: Rh, blue: N, red: O). Efficient
energy transfer from the Ru-based MLCT
levels to the lower-lying level involving
the Rh dimer takes place at room
Supramolecular Chemistry
A question of orientation: The selfassembly of a dialkynylene-bridged zinc
pyridylporphyrin dimer with rotational
freedom preferentially leads to a cyclic
tetramer consisting of the perpendicular
conformer (? ), rather than the more
usual planar conformer ( // , see picture).
This preference most likely arises from an
efficient cancellation of dipole moments
in the self-assembled structure.
Asymmetric cyclopropanation and
monobenzoylation reactions of meso diols
employing borabox catalysts 1 (M = Cu)
result in high enantioselectivities. The
borabox ligands are anionic analogues of
the bisoxazolines 2 and are readily prepared by lithiation of oxazolines and
subsequent trapping with boron halides.
A. Tsuda,* H. Hu, R. Tanaka,
T. Aida*
4884 ? 4888
Planar or Perpendicular? Conformational
Preferences of p-Conjugated
Metalloporphyrin Dimers and Trimers in
Supramolecular Tubular Arrays
N Ligands
C. Mazet, V. KQhler,
A. Pfaltz*
The considerable potential of borabox
ligands in asymmetric catalysis is shown.
4888 ? 4891
Chiral Boron-Bridged Bisoxazolines:
Readily Available Anionic Ligands for
Asymmetric Catalysis
Host?Guest Chemistry
D. Garozzo, G. Gattuso, A. Notti,
A. Pappalardo, S. Pappalardo,*
M. F. Parisi,* M. Perez,
I. Pisagatti
4892 ? 4896
The anions went in two by two: Separate
ion-pair binding of nano-sized a,walkanediyldiammonium dichloride salts is
achieved in organic media with high
efficiency and selectivity by a heterotetratopic receptor that comprises two
Angew. Chem. Int. Ed. 2005, 44, 4818 ? 4827
converging calix[5]arene units to tightly
encapsulate the linear dication, as well as
two ureido side functions to simultaneously bind the chloride counteranions
through hydrogen bonding (see picture).
A Calix[5]arene-Based Heterotetratopic
Host for Molecular Recognition of
Long-Chain, Ion-Paired
a,w-Alkanediyldiammonium Salts
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Supramolecular Chemistry
A. Hori, T. Sawada, K. Yamashita,
M. Fujita*
4896 ? 4899
Ultramacrocyclization through Reversible
Extreme macrocyclization! An ultramacrocyclic structure with 238 non-hydrogen
atoms in its backbone is obtained quantitatively through the reversible catenation
of a double-loop compound that contains
PdII-clipped coordination rings at both
ends (see structure). The PdII ring can be
regarded as a nanoscale reaction center
that is available for connecting nanoscopic components without high entropy
Switchable Molecules
S. Hayami,* Y. Shigeyoshi, M. Akita,
K. Inoue, K. Kato, K. Osaka, M. Takata,
R. Kawajiri, T. Mitani,
Y. Maeda
4899 ? 4903
Reverse Spin Transition Triggered by a
Structural Phase Transition
Reverse spin crossover (RSCO), the
reversible spin transition from the high- to
the low-spin state upon heating, was
observed in [Co(Cn-terpy)2](BF4)2 (Cn-terpy = terpyridine) equipped with a long
Medicinal Chemistry
alkoxy chain (AC) of n = 14 or 16 methylene units (see picture). The wide thermal
hysteresis of the RSCO around room
temperature could allow such compounds
to be used as molecular switches.
Antimalarial compounds: Structurally
simple acyclic inhibitors of protein farnesyltransferase (active-site model shown)
from the malaria parasite Plasmodium
falciparum may allow third world countries
access to an effective and inexpensive
antimalarial therapy to counter the estimated half billion infections that occur
M. P. Glenn, S.-Y. Chang, O. Hucke,
C. L. M. J. Verlinde, K. Rivas, C. Horn7y,
K. Yokoyama, F. S. Buckner, P. R. Pendyala,
D. Chakrabarti, M. Gelb,
W. C. Van Voorhis, S. M. Sebti,
A. D. Hamilton*
4903 ? 4906
Structurally Simple Farnesyltransferase
Inhibitors Arrest the Growth of Malaria
Main Group Chemistry
H. V. R. Dias,* S. Singh,
T. R. Cundari
4907 ? 4910
Monomeric Thallium(i) Complexes of
Fluorinated Triazapentadienyl Ligands
Rare examples of thallium monocoordination? Polyfluorinated triazapentadienes
HN[C(C3F7)NAr]2 with bulky aryl substituents react with TlOEt to give rare, monomeric thallium(i) complexes in which the
TlI center coordinates to the central nitrogen atom of the W-shaped triazapentadienyl ligand system (see figure;
Ar = 2,4,6-trimethylphenyl; N: blue,
F: yellow, Tl: green).
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2005, 44, 4818 ? 4827
Unfolding upon dehydration:. What happens to the structure of a native protein
that is suddenly exposed to vacuum?
Native electron capture dissociation
shows that dehydration turns the strongest intramolecular interactions in solution into the weakest in the gas phase.
Radical transfer hydroaminations have
been achieved with 3-aminated 1,4-cyclo-
Meet on the edge: The relative concentration of corner and edge ions in a
cubelike nanoparticle critically depends
on the size of the nanoparticle. On MgO
nanocubes this ratio is reflected by their
optical properties (see picture).
hexadienes rather than transition-metal
reagents (see scheme; DTBP = di-tertbutylperoxide). These functionalized
cyclohexadienes are efficient N-radical
precursors. Moreover, they are stable and
readily prepared, and radical generation
occurs under neutral conditions.
Mass Spectrometry of Proteins
K. Breuker,*
F. W. McLafferty
4911 ? 4914
The Thermal Unfolding of Native
Cytochrome c in the Transition from
Solution to Gas Phase Probed by Native
Electron Capture Dissociation
Radical Chemistry
J. Kemper, A. Studer*
4914 ? 4917
Stable Reagents for the Generation of
N-Centered Radicals: Hydroamination of
S. Stankic, M. M'ller, O. Diwald,
M. Sterrer, E. KnQzinger,*
J. Bernardi
4917 ? 4920
Size-Dependent Optical Properties of
MgO Nanocubes
The intermediately generated Li[(Me3Si)2CHSb(H)] reacts with
[(N3N)WCl] to give the first complex with
a terminal stibido ligand, [(N3N)WSb]
(see structure). Spectroscopic features
and the X-ray structure of this product
clearly reveal the triple-bond character of
the WSb bond. A comparison of the
bonding situations in the series
[(N3N)WE] (E = P, As, Sb, Bi) indicates
only a weak polarization of the triple bond.
Angew. Chem. Int. Ed. 2005, 44, 4818 ? 4827
Pnicogen Complexes
G. BalTzs, M. Sierka,
M. Scheer*
4920 ? 4924
Antimony?Tungsten Triple Bond: A Stable
Complex with a Terminal Antimony Ligand
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Natural Products Synthesis
K. C. Nicolaou,* D. W. Kim, D. Schlawe,
D. E. Lizos, R. G. de Noronha,
D. A. Longbottom
4925 ? 4929
Total Synthesis of Halipeptins A and D
and Analogues
Deceptive rings: Halipeptins A (1 a) and
D (1 b) and analogues thereof were synthesized from fragments 2 and 3 a, b,
respectively. Key steps included peptidebond formation, DAST-induced thiazoline
construction, and macrolactamization.
B. A. Seigal, M. H. An,
M. L. Snapper*
4929 ? 4932
Intramolecular [2�] Cycloadditions
with (Cyclobutadiene)tricarbonyliron
Highly functionalized strained rings are
prepared through the cycloaddition of
cyclobutadiene to alkynes. An intramolecular [2�] cycloaddition is optimized
Unlike the naturally isolated (and possibly
contaminated) material, synthetic 1 b
exhibited only weak toxicity against tumor
cells. DAST = (diethylamino)sulfur trifluoride.
for a variety of (cyclobutadiene)tricarbonyliron substrates with tethered alkynyl
units (see scheme; CAN = cerium(iv)
ammonium nitrate). The nature of the
tether between the reactive functional
groups in this transformation is found to
have a significant influence on the outcome.
Asymmetric Catalysis
C.-J. Wang, X. Sun,
X. Zhang*
4933 ? 4935
Enantioselective Hydrogenation of
Allylphthalimides: An Efficient Method for
the Synthesis of b-Methyl Chiral Amines
High yields and up to 98 % ee have been
achieved by asymmetric hydrogenation of
allylphthalimides followed by hydrolysis to
give b-methyl chiral amines by using a
Ru?C3-tunephos catalyst (see scheme).
The synthetic utility of this procedure has
been demonstrated through the synthesis
of the key intermediate of the LTs receptor
antagonist (Zeneca ZD 3532).
Salen?s lot: Meerwein?Ponndorf?Verley
reduction of [Ti(salen)(OiPr)2] (salen =
bis(salicylidene)ethylenediaminato) complexes followed by treatment with water
leads to the synthesis of pseudo-heterochiral and homochiral di-m-oxotitanium
dimers. These dimers, in particular
(aR,S,D, aR,S,D)-dimer 1, efficiently catalyze the epoxidation of simple olefins
using aqueous hydrogen peroxide (see
scheme) with ee values up to 99 % and
turnover numbers up to 4600.
Asymmetric Catalysis
K. Matsumoto, Y. Sawada, B. Saito,
K. Sakai, T. Katsuki*
4935 ? 4939
Construction of Pseudo-Heterochiral and
Homochiral Di-m-oxotitanium(Schiff
base) Dimers and Enantioselective
Epoxidation Using Aqueous Hydrogen
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2005, 44, 4818 ? 4827
Protein Models
One good turn: b-Turns are an important
component of protein structure and
nucleation sites for b-hairpin folding. With
ubiquitin as a ?host? system (see structure), protein engineering methods have
been used to determine the energetic
contribution of type I? b-turns to the
stability of proteins, with a view to
optimizing the rational design of model
peptide systems.
E. R. Simpson, J. K. Meldrum, R. Bofill,
M. D. Crespo, E. Holmes,
M. S. Searle*
4939 ? 4944
Engineering Enhanced Protein Stability
through b-Turn Optimization: Insights for
the Design of Stable Peptide b-Hairpin
Natural Product Synthesis
F. W. Lichtenthaler,* E. Cuny,
O. Sakanaka
4944 ? 4948
Spectinomycin and the gomphosides:
Use of 6-deoxyhexulosyl derivatives of dglucose in Ag2CO3-mediated glycosylation
of gomphogenin and actinamine has
allowed the first syntheses of cardiac
glycosides with ring A-annulated sugar
components (see picture; Bz = benzoyl)
and an alternate synthesis of the antibiotic
A Concise and General Method for Doubly
Attaching 2-Ketosugars to Aglycon Diols:
Synthesis of the Gomphosides and
Catalytic Tandem Reactions
E. Genin, S. Antoniotti, V. Michelet,*
J.-P. Gen辴*
4949 ? 4953
An efficient, selective, and atom-economical access to ketal building blocks is
provided by the title reaction (see
scheme). The entire process occurs
Angew. Chem. Int. Ed. 2005, 44, 4818 ? 4827
smoothly in the presence of a catalytic
amount of [{Ir(cod)Cl}2] at room temperature in methanol, ethanol, or allyl
alcohol as solvents.
An IrI-Catalyzed exo-Selective Tandem
Cycloisomerization/Hydroalkoxylation of
Bis-Homopropargylic Alcohols at Room
Facile formation of the ditelluride
[(TePiPr2NiPr2PTe-)2], which exists as a
centrosymmetric dimer (see picture: Te
green, P purple, N blue, C gray) with a
weak TeTe bond, embodies a new feature
of the chemistry of dichalcogenoimidodiphosphinate ligands. The monotelluride HPiPr2NiPr2PTe analogue is
obtained as the PH tautomer.
Main Group Chemistry
T. Chivers,* D. J. Eisler, J. S. Ritch,
H. M. Tuononen
4953 ? 4956
An Unusual Ditelluride: Synthesis and
Molecular and Electronic Structures of the
Dimer of the Tellurium-Centered Radical
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
High-aspect-ratio, monocrystalline cadmium chloride nanowires doped with
fluorescent CdS nanoparticles have been
synthesized using planar lipid membranes as templates (see picture). Cd2+
ions bound to the lipid bilayers (a) are
released at low pH to the nanometersized, interlamellar water films (b) where
the sudden increase in concentration
leads to the formation of nanowires (c)
that show excellent light-waveguiding
G. Gopalakrishnan, J.-M. Segura,
D. Stamou, C. Gaillard, M. Gjoni,
R. Hovius, K. J. Schenk, P. A. Stadelmann,
H. Vogel*
4957 ? 4960
Synthesis of Nanoscopic Optical Fibers
Using Lipid Membranes as Templates
Coordination Modes
J. V. Kingston, A. Ellern,
J. G. Verkade*
4960 ? 4963
A Stable Structurally Characterized
Phosphorus-Bound Isocyanide and Its
Thermal and Catalyzed Isomerization to
the Corresponding Cyanide
Ring-Opening Polymerization
O. Coulembier, A. P. Dove, R. C. Pratt,
A. C. Sentman, D. A. Culkin, L. Mespouille,
P. Dubois,* R. M. Waymouth,*
J. L. Hedrick*
4964 ? 4968
Latent, Thermally Activated Organic
Catalysts for the On-Demand Living
Polymerization of Lactide
A PNC linkage has been realized by the
formation of a stable isocyano azaphosphatranium ion with a facile synthesis.
Subsequent thermal or Lewis acid catalyzed isomerization of the isocyanide
derivative to its cyanide isomer (see
scheme) was carried out and followed by
P NMR spectroscopy. Both compounds
were characterized by X-ray crystallography.
It?s all about control: Alcohol adducts of
stable N-heterocyclic carbenes function as
excellent single-component catalysts/
initiators for the ring-opening polymerization of lactide (see scheme). This
polymerization can be reversibly terminated simply by modulating the temperature. The use of multifunctional macro-
initiators enables the synthesis of more
complex polymer architectures.
From linear to folded simply by CH贩稯
bonding: A new low-temperature photoelectron spectroscopy apparatus is used
to study hydrogen bonding between
unactivated alkanes and a carboxylate
group. Gaseous linear carboxylates 1,
CH3(CH2)nCO2, assume folded structures 2 at low temperatures by weak
CH贩稯 hydrogen bonding between the
terminal CH3 and CO2 groups for n 5.
Hydrogen Bonding
X.-B. Wang, H.-K. Woo, B. Kiran,
L.-S. Wang*
4968 ? 4972
Observation of Weak CH贩稯 Hydrogen
Bonding to Unactivated Alkanes
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2005, 44, 4818 ? 4827
g-Peptide Structures
P. G. Vasudev, N. Shamala,* K. Ananda,
P. Balaram*
4972 ? 4975
Nine is the number: Novel C9-hydrogenbonded structures (in which the hydrogen
bonds enclose a ring of nine atoms) are
observed in protected di- and tetrapep-
tides formed by the g-amino acid residue
gabapentin. The structures reveal new
families of C9 helices and ribbons (see
structure) in g-polypeptides.
C9 Helices and Ribbons in g-Peptides:
Crystal Structures of Gabapentin
Chemical Biology
It works both ways: The development of
potent peptidomimetic acyl protein
thioesterase 1 (APT1) inhibitors, such as
Raspalin 3 (see structure), and their use in
biological and biochemical investigations
are reported. The results show that the
enzyme can deacylate and acylate Ras
P. Deck, D. Pendzialek, M. Biel,
M. Wagner, B. Popkirova, B. Ludolph,
G. Kragol, J. Kuhlmann,* A. Giannis,*
H. Waldmann*
4975 ? 4980
Development and Biological Evaluation of
Acyl Protein Thioesterase 1 (APT1)
Carbene Complexes
J. Barluenga,* R. B. de la R?a, D. de STa,
A. Ballesteros, M. TomTs
4981 ? 4983
A single (or iterative) insertion of alkyne
units into metal carbene complexes,
accompanied by alkoxy exchange, occurs
readily to give elusive alkynyl-
(alkoxy)carbenes (see scheme) as well as
polyalkynyl(alkoxy)carbenes. M = W, Cr,
Mo. TMSOTf = trimethylsilyl trifluoromethanesulfonate.
Formal Alkyne Insertion into
Alkoxycarbene Complexes: Simple Access
to Enantiopure Group 6
Alkynyl(alkoxy)carbene Complexes
Angew. Chem. Int. Ed. 2005, 44, 4818 ? 4827
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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