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Graphical Abstract Angew. Chem. Int. Ed. 382005

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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:
Sheereen Majd, Michael Mayer*
Hydrogel-Stamping of Arrays of Supported Lipid Bilayers with
Various Lipid Compositions for Screening of Drug–Membrane
and Protein–Membrane Interactions
Yoshitaka Ishibashi, Yuhki Bessho, Masahiro Yoshimura,
Masaki Tsukamoto, Masato Kitamura*
Origin of the Minor Enantiomeric Product in a Noyori
Asymmetric Hydrogenation
Holger Braunschweig,* Thomas Herbst, Daniela Rais, Fabian Seeler
Synthesis of Borirenes by Photochemical Borylene Transfer from
[(OC)5M=BN(SiMe3)2] (M = Cr, Mo) to Alkynes
Y. Andrew Yang, Huimeng Wu, K. R. Williams, Y. Charles Cao*
Synthesis of CdSe and CdTe Nanocrystals without Precursor
Masayuki Nihei, Mayumi Ui, Mizuho Yokota, Lingqin Han,
Atsushi Maeda, Hideo Kishida, Hiroshi Okamoto, Hiroki Oshio*
Two-Step Spin Conversion in a Cyanide-Bridged Ferrous Square
Sean F. Brady,* Jon Clardy
Cloning and Heterologous Expression of Isonitrile Biosynthetic
Genes from Environmental DNA
Meeting Reviews
ADHOC 2005 in Cologne: The Latest in Dioxygen Activation and
Homogeneous Catalytic Oxidation
C. Limberg*
reviewed by P. Kraft
Books for the (Chemical) Senses
Odor Perception
R. Axel*
6111 – 6127
Scents and Sensibility: A Molecular Logic
of Olfactory Perception (Nobel Lecture)
L. B. Buck*
6128 – 6140
A sense of occasion: Around 20 years after
the start of their pioneering studies on the
function of the nose and brain in odor
perception, R. Axel and L. Buck have
received the 2004 Nobel Prize for Medicine or Physiology. The picture shows
schematically the coding of different
odors in the olfactory epithelium (OE) and
olfactory bulb (OB).
Unraveling the Sense of Smell (Nobel
Coordination Chains
T. Classen,* G. Fratesi, G. Costantini,
S. Fabris,* F. L. Stadler, C. Kim,
S. de Gironcoli, S. Baroni,
K. Kern*
6142 – 6145
Templated Growth of Metal–Organic
Coordination Chains at Surfaces
Line them up: Metal–organic chains (see
scanning tunneling microscopy image)
have been created in situ by self-organized growth at a metal surface under
ultrahigh vacuum. These 1D arrangements of metal centers (Fe, Cu), regularly
spaced by organic linkers such as trimesitylic acid, open new possibilities for the
study of low-dimensional magnetism.
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2005, 44, 6090 – 6099
Reaction Mechanisms
Support for the direct route: That cyclobutenes are not necessary intermediates
in the skeletal rearrangement of enynes is
supported by DFT calculations and kinetic
studies. Cyclobutenes may arise from
the corresponding syn-cyclopropylgold(i)
carbenes (see scheme).
That’s quite a switch! The ionizationinduced switch in the preferred intermolecular binding motif of the phenol···Ar
interaction from p bonding to hydrogen
bonding (see picture) has been monitored
in real time by time-resolved picosecond
UV-UV-IR pump-probe spectroscopy. The
timescale for this prototypical intermolecular hydrophobic!hydrophilic (p!H)
isomerization process (10 ps) has been
measured for the first time.
The liquid–solid transition: Automatic
assignment of solid-state NMR data as
well as fast and accurate calculation of the
structure of immobilized proteins at
atomic resolution can be achieved by
using the program SOLARIA (a modification of the ARIA protocol). The picture
shows the lowest energy structures of the
a-spectrin SH3 domain calculated by
SOLARIA (blue) overlaid with the X-ray
crystal structure (red).
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USA by Publications Expediting Inc. 200
Meacham Ave., Elmont, NY 11003. Periodicals
Angew. Chem. Int. Ed. 2005, 44, 6090 – 6099
C. Nieto-Oberhuber, S. L8pez,
M. P. Mu9oz, D. J. C;rdenas, E. Bu9uel,
C. Nevado,
A. M. Echavarren*
6146 – 6148
Divergent Mechanisms for the Skeletal
Rearrangement and [2þ2] Cycloaddition
of Enynes Catalyzed by Gold
Molecular Dynamics
S. Ishiuchi, M. Sakai, Y. Tsuchida,
A. Takeda, Y. Kawashima, M. Fujii,*
O. Dopfer,*
K. MAller-Dethlefs*
6149 – 6151
Real-Time Observation of IonizationInduced Hydrophobic!Hydrophilic
Structure Elucidation
M. Fossi, F. Castellani, M. Nilges,
H. Oschkinat,*
B.-J. van Rossum*
6151 – 6154
SOLARIA: A Protocol for Automated
Cross-Peak Assignment and Structure
Calculation for Solid-State Magic-Angle
Spinning NMR Spectroscopy
Caught in a barrel: AFM studies indicate
that the host–guest complexes formed
between b-barrel pores and polymer
blockers are pseudorotaxanes. The nonstatistical location of the contracted
supramolecular barrels on the polymers
indicates that the sticky polymer templates insert quickly into the b barrels (see
schematic representation) and then
undergo slow motion through the barrels.
Molecular Recognition
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J. Kumaki,* E. Yashima, G. Bollot,
J. Mareda, S. Litvinchuk,
S. Matile*
6154 – 6157
AFM Snapshots of Synthetic
Multifunctional Pores with Polyacetylene
Blockers: Pseudorotaxanes and Template
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Synthetic Methods
J. S. Clark,* M. C. Kimber, J. Robertson,
C. S. P. McErlean, C. Wilson 6157 – 6162
d-glucal is the starting point for the
efficient synthesis of the F–J fragment of
the gambieric acids (see scheme). The Hring diol was subjected to double twodirectional alkynyl ether formation, carbocupration ring-closing metathesis, and
hydroboration. The tricyclic G–I diol was
then converted into the F–J fragment by a
sequence that involves another double
two-directional ring-closing metathesis
Rapid Two-Directional Synthesis of the F–J
Fragment of the Gambieric Acids by
Iterative Double Ring-Closing Metathesis
Enzyme Modeling
E. Bourles, R. Alves de Sousa, E. Galardon,
M. Giorgi, I. Artaud*
6162 – 6165
Cyclic pseudopeptidic thiosulfinates
reveal a new type of reaction that may be
important in biological systems. It
involves hydrolytic cleavage of the S(O)S
bond on 1 followed by metalation to form
a dissymmetrical CoIII complex with a
mixed diamidato-N, thiolato-S, sulfinato-S
donor set in 2 that is related to the nitrile
hydratase active site.
Highly efficient: Tetraarylphosphonium
halides, Ar4P+X, as arylating reagents
efficiently deliver an aryl group in Pdcatalyzed reactions with olefins, organoboron compounds, and terminal alkynes
(see scheme).
The benzhydryl group is the key: Efficient
alkylation of 3-substituted aziridine-2-carboxylates is only possible with N-benzhydryl-protected aziridines and occurs with
complete retention of the configuration at
the 2-position. Sequential catalytic asymmetric aziridination and aziridine alkylation reactions have been applied to the
synthesis of BIRT-377 (see structure).
Angew. Chem. Int. Ed. 2005, 44, 6090 – 6099
Direct Synthesis of a Thiolato-S and
Sulfinato-S CoIII Complex Related to the
Active Site of Nitrile Hydratase: A Pathway
to the Post-Translational Oxidation of the
Synthetic Methods
L. K. Hwang, Y. Na, J. Lee, Y. Do,
S. Chang*
6166 – 6169
Tetraarylphosphonium Halides as
Arylating Reagents in Pd-Catalyzed Heck
and Cross-Coupling Reactions
Synthetic Methods
A. P. Patwardhan, V. R. Pulgam, Y. Zhang,
W. D. Wulff*
6169 – 6172
Highly Diastereoselective Alkylation of
Aziridine-2-carboxylate Esters:
Enantioselective Synthesis of LFA-1
Antagonist BIRT-377
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
C–C Coupling Reactions
K. W. Anderson,
S. L. Buchwald*
6173 – 6177
General Catalysts for the Suzuki–Miyaura
and Sonogashira Coupling Reactions of
Aryl Chlorides and for the Coupling of
Challenging Substrate Combinations in
Amphiphilic phosphine ligands (see
structures; Cy = cyclohexyl) were prepared
and utilized in palladium-catalyzed
Suzuki–Miyaura and Sonogashira coupling reactions in water or water/organic
biphasic solvents, providing excellent
yields of functionalized biaryls and aryl
alkynes, respectively.
Stereoselective Butenolide Reduction
M. P. Rainka, J. E. Milne,
S. L. Buchwald*
Only six steps were needed for the total
synthesis of eupomatilone-3 in 48 %
overall yield thanks to the development of
a dynamic kinetic resolution that allowed
the reductive conversion of a racemic a,bunsaturated butenolide in high yield and
high enantiomeric and diastereomeric
excess. This copper-catalyzed dynamic
kinetic resolution was then applied to
several g-aryl-containing a,b-unsaturated
6177 – 6180
Dynamic Kinetic Resolution of
a,b-Unsaturated Lactones through
Asymmetric Copper-Catalyzed Conjugate
Reduction: Application to the Total
Synthesis of Eupomatilone-3
Helical Structures
Let’s twist again: A cation–p interaction
between Trp and Arg is designed at the
interface between two a helices of a
coiled-coil structure and stabilizes the
structure more than Glu and Lys ion-pair
interactions. Two or three Trp–Arg sets
form an extended array of interactions
(see picture) and increase the melting
temperature of the peptide.
Y. Sakurai, T. Mizuno, H. Hiroaki,
K. Gohda, J.-i. Oku,
T. Tanaka*
6180 – 6183
High Thermal Stability Imparted by a
Designed Tandem Arg–Trp Stretch in an
a-Helical Coiled Coil
Synthetic Methods
S. Kim, S. Kim,* N. Otsuka,
I. Ryu*
6183 – 6186
Tin-Free Radical Carbonylation: Thiol
Ester Synthesis Using Alkyl Allyl Sulfone
Precursors, Phenyl Benzenethiosulfonate,
and CO
Remove contents from tin … Thiol esters
have been successfully synthesized
through tin-free radical carbonylation (see
scheme; V-40 = initiator). This approach
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
can be further extended to sequential
radical reactions involving cyclization,
carbonylation, and trapping of acyl radicals by phenyl benzenethiosulfonate.
Angew. Chem. Int. Ed. 2005, 44, 6090 – 6099
Enantioselective Synthesis
C. Palomo,* M. Oiarbide, E. Arceo,
J. M. GarcQa, R. L8pez, A. Gonz;lez,
A. Linden
6187 – 6190
A fine pair: Excellent levels of regio-, endo/
exo-, diastereo-, and/or enantioselectivity
are attained in the Cu-catalyzed cycloaddition of nitrones with a’-hydroxy enones
(see scheme). The resulting adducts can
be further elaborated to the corresponding isoxazolidines bearing aldehyde,
ketone, and carboxylic acid functions.
Lewis Acid Catalyzed Asymmetric
Cycloadditions of Nitrones: a’-Hydroxy
Enones as Efficient Reaction Partners
Tandem Reactions
M. Ueda, H. Miyabe, H. Sugino, O. Miyata,
T. Naito*
6190 – 6193
The direct generation of boryl enamine 2
by radical addition to the chiral a,bunsaturated oxime ether 1 (X = (1R)camphorsultam, Bn = benzyl) followed by
reaction with aldehydes gave rise to a
tandem carbon–carbon bond-forming
method, yielding lactones 3. The result is
a novel asymmetric synthesis of g-butyrolactones and g-amino acids by way of both
a radical and an ionic process.
Tandem Radical-Addition–Aldol-Type
Reaction of an a,b-Unsaturated Oxime
A new and effective use of hypervalent
iodine(iii) reagents as catalysts involves
the transformation of iodoarenes 1 into
hypervalent iodine(iii) species 2 with
meta-chloroperbenzoic acid (mCPBA) as
the appropriate cooxidant. With observed
turnover numbers greater than 70, this
procedure paves the way for broader
application of these useful oxidants in
organic synthesis.
Catalytic Oxidation
Methylation or phosphenium insertion
reactions with cyclopolyphosphines
(PtBu)3 or (PCy)4 (Cy = cyclohexyl) are
presented as stereospecific and highyielding preparative approaches to cyclopolyphosphinophosphonium cations. The
cations [(PtBu)3Me]+, [(PCy)4Me]+, and
[(PtBu)3PMe2]+ (see picture; P orange,
C gray) are prepared as trifluoromethanesulfonate salts and represent key
frameworks in fundamental catena-phosphorus chemistry.
Angew. Chem. Int. Ed. 2005, 44, 6090 – 6099
T. Dohi, A. Maruyama, M. Yoshimura,
K. Morimoto, H. Tohma,
Y. Kita*
6193 – 6196
Versatile Hypervalent-Iodine(iii)Catalyzed Oxidations with
m-Chloroperbenzoic Acid as a Cooxidant
Phosphorus Cations
N. Burford,* C. A. Dyker, M. Lumsden,
A. Decken
6196 – 6199
Small Cyclopolyphosphinophosphonium
Cations: Systematic Development of
Fundamental catena-Phosphorus
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Actinide Chemistry
G. Tian, J. Xu, L. Rao*
6200 – 6203
Optical Absorption and Structure of a
Highly Symmetrical Neptunium(v)
Diamide Complex
A reflection on neptunium absorption:
The absorption spectrum of NpV around
980 nm originates from a 5f!5f electricdipole transition, which is allowed if the
NpV ion lies in a coordination environment that lacks a center of inversion, such
as in [NpO2(H2O)5]+. However, the transition is completely forbidden by
Laporte’s rule in the highly symmetrical
NpV diamide complex [NpO2(L)2]+ (see
structure; Np green, O red, N blue,
C gray).
Imido Complexes
M. M. Abu-Omar,* C. E. Shields,
N. Y. Edwards, R. A. Eikey
6203 – 6207
On the Mechanism of the Reaction of
Organic Azides with Transition Metals:
Evidence for Triplet Nitrene Capture
High-valent imido complexes are
obtained by reaction of the manganese(iii) corrole [Mn(tpfc)] with aryl azides by
a novel reaction mechanism in which
singlet nitrene undergoes intersystem
crossing to the triplet state, which is
trapped by the metal corrole, in competition with dimerization to the azo compound (see scheme).
Energy transfer at the interface of two
dissimilar conjugated polymer chains (see
picture; DMOS = 2-dimethyloctylsilyl-pphenylenevinylene; MEH = 2-methoxy-5(2’-ethylhexyloxy)-p-phenylenevinylene)
has been studied using single-molecule
spectroscopy. Morphological features
control energy-transfer processes between
the blocks and lead to strongly heterogeneous efficiencies of energy transfer.
Conjugated Polymers
J. K. Grey, D. Y. Kim, Y. J. Lee,
J. J. Gutierrez, N. Luong, J. P. Ferraris,
P. F. Barbara*
6207 – 6210
Single-Molecule Studies of Electronic
Energy Transfer in a Diblock Conjugated
DNA Cleavage
M. Roginskaya, Y. Razskazovskiy,
W. A. Bernhard*
6210 – 6213
2-Deoxyribonolactone Lesions in
X-ray-Irradiated DNA: Quantitative
Determination by Catalytic 5-Methylene2-furanone Release
Torn genes: DNA tetramers containing the
2-deoxyribonolactone (dL) lesion have
been isolated by HPLC from d(CGCG) and
d(pCGCG) films irradiated with X-rays.
Upon treatment with spermine as a
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
catalyst, the dL-containing tetramers
decompose to 5-methylene-2-furanone (5MF; see scheme), a characteristic product
of dL decomposition. Hence, 5-MP can be
used to quantify dL lesions in DNA.
Angew. Chem. Int. Ed. 2005, 44, 6090 – 6099
Very low loading and short reaction times
are characteristic features of the quantitative reduction of different ketones using
2-propanol and terdentate [RuX(CNN)(dppb)] (X = H, Cl (see structure);
dppb = Ph2P(CH2)4PPh2) complexes prepared from 6-(4’-methylphenyl)-2-pyridylmethylamine. The reduction apparently
takes place by reversible insertion of the
substrate into the RuH bond, thus
leading to a RuII alkoxide.
Homogeneous Catalysis
W. Baratta,* G. Chelucci, S. Gladiali,
K. Siega, M. Toniutti, M. Zanette,
E. Zangrando, P. Rigo
6214 – 6219
Ruthenium(ii) Terdentate CNN
Complexes: Superlative Catalysts for the
Hydrogen-Transfer Reduction of Ketones
by Reversible Insertion of a Carbonyl
Group into the RuH Bond
Synthetic Methods
G. Bartoli,* M. Bosco, A. Carlone,
M. Locatelli, P. Melchiorre,*
L. Sambri
6219 – 6222
No metal required: A protocol for the
enantioselective organocatalytic chlorination of cyclic and acyclic b-keto esters and
cyclic b-diketones has been developed
which is also effective for the asymmetric
bromination of b-keto esters. The methodology employs an inexpensive organocatalyst (e.g. benzoylquinidine) and polyhalogenated quinolinones as the source of
the halogen (see scheme).
The dual in the crown: The same compound can adopt two different, nonequilibrium tautomeric structures. This
unique structural dualism is demonstrated by the isolation of pure tautomeric
pairs, 7-RR’NH-7,8,9-C3B8H10 (zwitterionic) and 7-RR’N-7,8,9-C3B8H11 (neutral)
(where R,R’ = H or alkyls, see scheme,
PNT = proton nontransferring, PT = proton transferring) in the tricarbollide series.
Organocatalytic Asymmetric
a-Halogenation of 1,3-Dicarbonyl
M. Bakardjiev, J. Holub, D. Hnyk,
I. CQsařov;, M. G. S. Londesborough,
D. S. Perekalin, B. ŠtQbr*
6222 – 6226
Structural Dualism in the Zwitterionic
7-RR’NH-nido-7,8,9-C3B8H10 Tricarbollide
Series: An Example of Absolute
A. Al-Harrasi, H.-U. Reißig* 6227 – 6231
Under control: Lewis acids induce an
unexpected rearrangement of 1,3-dioxolanyl-substituted 1,2-oxazines to provide
bicyclic compounds in a stereocontrolled
Angew. Chem. Int. Ed. 2005, 44, 6090 – 6099
manner. They are precursors for enantiopure carbohydrate mimetics containing 3aminotetrahydropyran or 4-aminooxepane
substructures (see scheme; Bn = benzyl).
Synthesis of Enantiopure Carbohydrate
Mimetics by Lewis Acid Catalyzed
Rearrangement of 1,3-DioxolanylSubstituted 1,2-Oxazines
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Natural Product Synthesis
P. Fischer, A. B. GarcQa Segovia,
M. Gruner, P. Metz*
6231 – 6234
A General Sultone Route to the
Pamamycin Macrodiolides—Total
Synthesis of Pamamycin-621A and
Sultones swing again: The first total
syntheses of the title antibiotics (see
scheme) were achieved by application of
sultone methodology. Since the final lactonizations with formation of the ester
linkage between C1’ and the oxygen sub-
Alkyl Complexes
M. Westerhausen,* G. Sapelza,
P. Mayer
6234 – 6237
Activation of a Zinc-Bound Ethyl Group by
Formation of a Zn-CEt-Ba Moiety and
Crystal Structure of [{(Me3Si)2N}Ba(thf)Zn2(m-Et)(m3-PSitBu3)2]2 with Bridging
Ethyl Substituents
Metal Nanoparticles
S. Hermes, M.-K. SchrYter, R. Schmid,
L. Khodeir, M. Muhler, A. Tissler,
R. W. Fischer, R. A. Fischer* 6237 – 6241
Metal@MOF: Loading of Highly Porous
Coordination Polymers Host Lattices by
Metal Organic Chemical Vapor
Copper Oligophosphanides
R. Wolf, E. Hey-Hawkins*
6241 – 6244
Synthesis and Molecular Structure of
the Cu4P8 Cage Compound
stituent on C8 proceeded with complete
epimerization at C2’, the more readily
available C2’ epimeric smaller fragments
could be used for streamlining the synthetic sequence.
The phosphane unit is deprotonated in the
reaction of dialkylzinc with H2PSitBu3 and
(thf)2Ba[N(SiMe3)2]2 to give the title compound (molecular structure shown),
which has a coordinatively unsaturated
barium center. In the absence of excess
THF, the zinc-bound alkyl groups are
activated by formation of Ba-CEt-Zn threecenter bonds.
Precursors and particles captured in a net:
Porous coordination polymers such as
MOF-5 are efficient gas storage devices
and are also able to absorb metal organic
chemical vapor deposition (MOCVD)
precursors (see picture, red: [(h5C5H5)Pd(h3-C3H5)]). These incorporated
compounds are easily reduced to give the
corresponding metal nanoparticles.
Applications in heterogeneous catalysis,
for instance, methanol synthesis or
hydrogenation, are described.
Plenty of phosphorus: The first CuI oligophosphanido complex [Cu4(P4Ph4)2(PCyp3)3] (1; Cyp = cyclo-C5H9), synthesized from [CuCl(PCyp3)2] and [Na2(thf)4(P4Ph4)], displays a remarkable cage
structure in the solid state. The central
Cu4P8 core of 1 (with appendant phosphane P atoms) is shown in the picture.
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2005, 44, 6090 – 6099
Sister Journals
6248 – 6249
New results have revealed that some
values given in this original contribution
are incorrect. The determined cloud point
of polymer 5 does not lie over 95 8C as
originally reported, but is actually 17 8C.
The previously observed high optical
transparency of a dispersion of polymer 5
was a result of the very small particle size
that resulted from ultrasonic treatment. In
light of this new result, the data for
cyclodextrin-free polymer 5 presented in
Table 1 and Figures 1, 2, and 3 are incorrect. In Table 1, the LCST value of polymer
5 of > 95 8C should be replaced by 17 8C,
Angew. Chem. Int. Ed. 2005, 44, 6090 – 6099
while the monomer ratio (n/m) for polymers 5 and 6 should now read as 20:1
instead of 1:20. In Figures 1 and 3, the
plotted data for polymer 5 in the absence
of cyclodextrin should be replaced by a
function which shows a turbidity point at
17 8C. In Figure 2, the LCST value of
> 95 8C should be corrected to 17 8C. In
the text, all passages that refer to the
cloud point of cyclodextrin-free polymer 5
are incorrect. However, all the other
presented data as well as the conclusion
remain valid.
Influence of Cyclodextrin Molecules on
the Synthesis and the Thermoresponsive
Solution Behavior of N-Isopropylacrylamide Copolymers with Adamantyl
Groups in the Side Chains
H. Ritter,* O. Sadowski,
E. Tepper
Angew. Chem. Int. Ed. 2003, 42
DOI 10.1002/anie.200250814
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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abstract, int, angel, chem, graphical, 382005
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