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Graphical Abstract Angew. Chem. Int. Ed. 472004

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Contents
The following Communications are available online (in Wiley InterScience). You can find them, as
well as forthcoming Reviews, Highlights, and Essays, at www.angewandte.org, under Early View.
J. W. Yang, M. T. Hechavarria Fonseca, B. List*:
A Metal-Free Transfer Hydrogenation: Organocatalytic Conjugate
Reduction of a,b-Unsaturated Aldehydes
DOI: 10.1002/anie.200461816
Published online: November 12, 2004
L. Kastrup, S. W. Hell*:
Absolute Optical Cross Section of Individual Fluorescent
Molecules
DOI: 10.1002/anie.200461337
Published online: November 19, 2004
M. T. Kieber-Emmons, R. Schenker, G. P. A. Yap, T. C. Brunold,
C. G. Riordan*:
Spectroscopic Elucidation of a Peroxo Ni2(m-O2) Intermediate
Derived from a Nickel(i) Complex and Dioxygen
DOI: 10.1002/anie.200460747
Published online: November 19, 2004
D. Fiedler, R. G. Bergman,* K. N. Raymond*:
Supramolecular Catalysis of a Unimolecular Transformation:
Aza-Cope Rearrangement within a Self-Assembled Host
DOI: 10.1002/anie.200461776
Published online: November 19, 2004
Articles judged by the referees or the editor as being either very important or very urgent are immediately edited, proof-read, and electronically
published once the manuscript has arrived in the editorial office in its final form. As long as there is no page number available these articles should
be cited in the following manner:
Author(s), Angew. Chem. Int. Ed., online publication date, DOI.
News
P. Yang Receives Pure Chemistry
Award
6406
Inorganic Chemistry Award
to W. J. Evans
6406
E. Iglesia Receives George A. Olah
Award
6406
Books
Organic Chemistry Principles and
Industrial Practice
Mark M. Green, Harold A. Wittcoff
reviewed by J. S. Siegel
6407
Protein Crystallography in Drug Discovery
Robert E. Babine, Sherin S. Abdel-Meguid
reviewed by L.-O. Essen
6408
The Nobel Price in Medicine this year went
to Richard Axel and Linda Buck, who
elucidated the molecular basis of the
olfactory reception of fragrances and the
neuronal preprocessing of information in
the olfactory system. From the viewpoint
of a chemist, these studies offer fascinating perspectives. For example, they enable
an understanding of the perception of
odors by transmembrane proteins (see
picture).
Highlights
Chemistry of Odor Perception
U. J. Meierhenrich,* J. Golebiowski,
X. Fernandez,
D. Cabrol-Bass
6410 – 6412
The Molecular Basis of Olfactory
Chemoreception
6394
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2004, 43, 6394 – 6403
Angewandte
Chemie
The kiss of death for a protein is to be
labeled with ubiquitin (Ub, see picture).
The protein can then be recognized and
degraded by the 26S proteasome, an
important target in drug research, as it
regulates the concentration of certain
proteins. Recognition by the proteasome
is hindered by two novel proteasome
inhibitors, ubistatins A und B, which were
identified through a chemical genetic
approach.
Proteasome Inhibitors
M. Biel, V. Wascholowski,
A. Giannis*
6414 – 6416
A Fatal Affair: The Ubiquitinylation of
Proteins
Essays
Noble gases and Nobel prizes: To mark
the 100th anniversary of the awarding of
the Nobel Prize to Lord Rayleigh (see
picture; right) and Sir William Ramsay
(left) for their discovery and characterization of the noble gases, tribute is paid to
two scientific greats whose work goes far
beyond their prize-winning discovery.
History of Science
J. M. Thomas*
6418 – 6424
Argon and the Non-Inert Pair: Rayleigh
and Ramsay
Reviews
For the USA and Canada:
ANGEWANDTE CHEMIE International
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Angew. Chem. Int. Ed. 2004, 43, 6394 – 6403
Room for one more: The genetic code of
life consists of 64 coding units that
control the incorporation of no more than
20 canonical amino acids in proteins—
enough space remains for codon reassignments, which render additional,
noncanonical amino acids (see picture)
translationally active substrates for the
protein biosynthesis machinery. This
review surveys methods, problems, and
perspectives of this genetic code
engineering.
Protein Biosynthesis
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www.angewandte.org
N. Budisa*
6426 – 6463
Prolegomena to Future Experimental
Efforts on Genetic Code Engineering by
Expanding Its Amino Acid Repertoire
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
6395
Angewandte
Chemie
Communications
Self-assembly of rod-coil molecules with
an ester linkage gave a honeycomblike
supramolecular structure with 3D hexagonal symmetry. Hydrolysis of the ester
linkages and removal of the coil segments
(light blue) from the perforated lamellar
structure afforded crystalline sheets (dark
blue) with in-plane arrays of nanopores
whose hydrophobic interiors entrap
nonpolar molecules.
Nanoporous Sheets
M. Lee,* M.-H. Park, N.-K. Oh, W.-C. Zin,
H.-T. Jung, D. K. Yoon
6465 – 6468
Supramolecular Crystalline Sheets with
Ordered Nanopore Arrays from SelfAssembly of Rigid-Rod Building Blocks
Nanobiotechnology
Switchable formation of materials:
DNA-modified gold nanoparticles can
aggregate reversibly by the employment of
“fueling” oligomers that hybridize with
the linker oligomers within the aggregated
nanoparticles (see scheme). This
approach paves the way to the generation
of programmable functional materials.
P. Hazarika, B. Ceyhan,
C. M. Niemeyer*
6469 – 6471
Reversible Switching of DNA–Gold
Nanoparticle Aggregation
Polymer Chemistry
X. Yang, F. Hua, K. Yamato,
E. Ruckenstein, B. Gong,* W. Kim,
C. Y. Ryu*
6471 – 6474
Supramolecular AB Diblock Copolymers
Hydrogen-bonded duplexes of incompatible polystyrene and poly(ethylene glycol)
chains have been prepared that show
microphase separation (see picture). Differential scanning calorimetric studies of
the phase transitions for these copolymers show that they behave like typical
covalently bonded diblock copolymers at
temperatures below 170 8C.
Radical Reactions
T. Kubo,* M. Sakamoto, M. Akabane,
Y. Fujiwara, K. Yamamoto, M. Akita,
K. Inoue, T. Takui,
K. Nakasuji*
6474 – 6479
A phenalenyl-based singlet biradical that
shows highly amphoteric redox properties
(see scheme) has been prepared by a
stepwise synthesis. Its singlet biradical
Angew. Chem. Int. Ed. 2004, 43, 6394 – 6403
character originates from a small
HOMO–LUMO gap, as suggested by
quantum chemical calculations and
experimental data.
www.angewandte.org
Four-Stage Amphoteric Redox Properties
and Biradicaloid Character of Tetra-tertbutyldicyclopenta[b;d]thieno[1,2,3-cd;
5,6,7-c’d’]diphenalene
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
6397
Contents
Inorganic Electrides
Z. Li, J. Yang,* J. G. Hou,
Q. Zhu
Yes or no? Mayenite without the clathrated oxygen can be classified as an inorganic electride based on combined
charge-density (see picture, A) and electron-localization-function (ELF) analysis
(B). Ionic chemical bonds are found to
form between extra electrons and the
positively charged crystal framework in
this material.
6479 – 6482
Is Mayenite without Clathrated Oxygen an
Inorganic Electride?
Chiral Coordination Polymer
Three types of channel—right- (R) and
left-handed (L) helical, and achiral (A)—
alternate along the c axis in the structure
of the title compound (see picture). The
catalytically active groups of the 1-phosphonomethylproline ligands are directed
into the channels, thus suggesting applications of this material in asymmetric
catalysis.
X. Shi, G. Zhu, S. Qiu,* K. Huang, J. Yu,
R. Xu
6482 – 6485
Zn2[(S)-O3PCH2NHC4H7CO2]2 :
A Homochiral 3D Zinc Phosphonate
with Helical Channels
Molecular Switches
D. W. Steuerman, H.-R. Tseng, A. J. Peters,
A. H. Flood, J. O. Jeppesen, K. A. Nielsen,
J. F. Stoddart,* J. R. Heath* 6486 – 6491
Molecular-Mechanical Switch-Based
Solid-State Electrochromic Devices
You only need eyes to appreciate the color
change that occurs in a polymer matrix
when the bistable rotaxane shown is
switched between its ground-state (green)
and metastable-state (red) co-conformers. Not only is an electrochromic
device within reach, but a universal
switching mechanism seems to be on
the cards.
Asymmetric Synthesis
C. Ogawa, M. Sugiura,
S. Kobayashi*
6491 – 6493
Stereospecific, Enantioselective Allylation
of a-Hydrazono Esters by Using Allyltrichlorosilanes with BINAP Dioxides as
Neutral-Coordinate Organocatalysts
Excellent diastereo- and enantioselectivities were obtained in the title reaction.
(E)-Crotylsilanes gave syn adducts,
6398
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
whereas anti adducts were obtained from
(Z)-crotylsilanes (see scheme).
Angew. Chem. Int. Ed. 2004, 43, 6394 – 6403
Angewandte
Chemie
Stereoselective Synthesis
T. G. Back,* J. E. Wulff
Both enantiomers of the antiviral agent
virantmycin were synthesized in a
sequence of reactions in which the key
steps were a highly stereoselective porcine
liver esterase(PLE) mediated desymmetrization of a prochiral diester and a
6493 – 6496
A Stereodivergent Synthesis of
Virantmycin by an Enzyme-Mediated
Diester Desymmetrization and a Highly
Hindered Aryl Amination
remarkably effective intramolecular aryl
amination of an ortho-substituted aryl
bromide with a highly hindered a-quaternary formamide (see retrosynthetic
scheme).
RNA Binding
F.-S. Liang, S.-K. Wang, T. Nakatani,
C.-H. Wong*
6496 – 6500
Targeting RNAs with Tobramycin
Analogues
A library of 4,6-linked analogues of the
drug tobramycin with various mono- or
diaminosugars attached to the 6-position
of the two-ring core has been prepared
(see scheme; Bn = benzyl, Tol = p-tolyl).
Angew. Chem. Int. Ed. 2004, 43, 6394 – 6403
The compounds were screened against
different disease-related RNAs, and several of the synthetic analogues showed a
high affinity and selectivity toward certain
RNA sequences.
Long-range steric interactions of the protecting groups of the 1,5-diol were harnessed for the successful atropselective
macrolactonization (A) in the synthesis of
the C-1027 chromophore framework (see
scheme). Subsequent LiN(SiMe3)2/CeCl3promoted acetylide addition to an aldehyde (B) in the setting of a rigid macrocycle formed the target nine-membered
ring system with a highly strained diyne.
Natural Products Synthesis
Powerful dithiane coupling (A) of two
fragments and subsequent macrocyclization by ring-closing metathesis (B) produced the entire 27-membered carbocycle
of (þ)-pinnatoxin A (1), a major toxic
principle responsible for outbreaks of
shellfish poisonings in China and Japan.
Natural Products Synthesis
www.angewandte.org
M. Inoue,* T. Sasaki, S. Hatano,
M. Hirama*
6500 – 6505
Synthesis of the C-1027 Chromophore
Framework through Atropselective
Macrolactonization
S. Sakamoto, H. Sakazaki, K. Hagiwara,
K. Kamada, K. Ishii, T. Noda, M. Inoue,*
M. Hirama*
6505 – 6510
A Formal Total Synthesis of
(þ)-Pinnatoxin A
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
6399
Contents
Biaryl Compounds
K. Tanaka,* G. Nishida, A. Wada,
K. Noguchi
6510 – 6512
Enantioselective Synthesis of Axially
Chiral Phthalides through Cationic
[RhI(H8-binap)]-Catalyzed Cross Alkyne
Cyclotrimerization
Lead Complexes
A. C. Filippou,* N. Weidemann,
G. Schnakenburg, H. Rohde,
A. I. Philippopoulos
6512 – 6516
Tungsten–Lead Triple Bonds: Syntheses,
Structures, and Coordination Chemistry of
the Plumbylidyne Complexes
trans-[X(PMe3)4WPb(2,6-Trip2C6H3)]
Easy access to axially chiral phthalides
that bear one or two oxymethylene functionalities is provided by an enantioselective cross alkyne cyclotrimerization in the
presence of the cationic complex [RhI{(S)H8-binap}]+. The axial chirality is introduced during the formation of the benzene ring with high enantioselectivity.
Plumb line: A series of compounds trans[L(PMe3)4WPb(2,6-Trip2C6H3)]n+ (n = 0:
L = Br, I; n = 1: L = PhCN, PMe3 ;
Trip = 2,4,6-iPr3C6H2 ; see structure of
L = PMe3 derivative) containing WPb
triple bonds is reported. Quantum-chemical analyses of the WPb bond in the
plumbylidyne complex [(PMe3)5WPb(2,6-Trip2C6H3)]+ confirm the electronic
analogy with Fischer-type carbyne complexes.
Cycloadditions
G. PriP, N. PrPvost, H. Twin,
S. A. Fernandes, J. F. Hayes,
M. Shipman*
6517 – 6519
A Lewis Acid Catalyzed Intramolecular
[4þ3] Cycloaddition Route to Polycyclic
Systems That Contain a Seven-Membered
Ring
Two simple steps, including a new intramolecular [4þ3] cycloaddition, are
required for the preparation of polycycles
that contain a seven-membered ring from
2-methyleneaziridines (see scheme). The
Oxidation
The complete catalytic cycle of CO oxidation with N2O is shown to occur on Ptn+
(see scheme); for Pt7+ it involves six
different elementary reactions. Poisoning
of the catalyst by sequential addition of
CO is observed. The extent of poisoning
can be adjusted with the ratio of N2O and
CO partial pressures.
O. P. Balaj, I. Balteanu,
T. T. J. Roßteuscher, M. K. Beyer,*
V. E. Bondybey*
6519 – 6522
Catalytic Oxidation of CO with N2O on
Gas-Phase Platinum Clusters
6400
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
diene component is introduced by
selective lithiation/alkylation at C3 of the
aziridine ring. Lewis acid catalyzed
cyclization leads to the products in good
yields with stereocontrol.
Angew. Chem. Int. Ed. 2004, 43, 6394 – 6403
Angewandte
Chemie
Dye Aggregates
H. Kashida, H. Asanuma,*
M. Komiyama
Seeing red: Aggregates in which methyl
red and naphthyl red moieties are stacked
alternately in a DNA duplex have been
prepared by hybridization of two DNA–
dye conjugates (see picture). A sharp
absorption band appears at 478 nm,
which is different from that of the individual dyes. A strong CD effect is also
induced by the interstrand heterostacking
of the dyes.
6522 – 6525
Alternating Hetero H Aggregation of
Different Dyes by Interstrand Stacking
from Two DNA–Dye Conjugates
Reaction Mechanisms
A. CTtP, A. A. Boezio,
A. B. Charette*
Mistaken identity: The active catalyst in
the highly selective Cu-catalyzed nucleophilic addition of diorganozinc reagents
to N-diphenylphosphinoylimines (see
scheme) does not contain the bis(phosphine) ligand 1 but rather the hemilabile
6525 – 6528
Evidence for the Structure of the
Enantioactive Ligand in the Phosphine–
Copper-Catalyzed Addition of Diorganozinc Reagents to Imines
monophosphine oxide 2. Ligand 1 is
oxidized when it is mixed with either
copper(ii) or copper(i) triflate. The
analogous reaction under nonoxidizing
conditions is slower and not enantioselective.
Asymmetric Synthesis
I. Ibrahem, J. Casas,
A. CUrdova*
A proline-catalyzed Mannich reaction
produces a-aminomethylated ketones in
high yield and with excellent ee values (see
scheme). The Mannich bases resulting
from this highly practical one-pot three-
6528 – 6531
Direct Catalytic Enantioselective
a-Aminomethylation of Ketones
component asymmetric reaction are of
particular interest, for example, as synthetic building blocks and precursors of
pharmaceutically valuable 1,3-amino
alcohols.
Oxidations
H. SundPn, M. Engqvist, J. Casas,
I. Ibrahem, A. CUrdova*
6532 – 6535
A possible prebiotic pathway for the
asymmetric incorporation of molecular
oxygen into organic compounds involves
the amino acid catalyzed reaction of
molecular singlet oxygen with ketones.
Angew. Chem. Int. Ed. 2004, 43, 6394 – 6403
Amino acids and their derivatives mediate
the reaction between oxygen and
ketones with high efficiency to produce
a-hydroxyketones (see scheme).
www.angewandte.org
Direct Amino Acid Catalyzed Asymmetric
a Oxidation of Ketones with Molecular
Oxygen
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
6401
Contents
Dynamic Kinetic Resolution
B. MartVn-Matute, M. Edin, K. BogWr,
J.-E. BXckvall*
6535 – 6539
Highly Compatible Metal and Enzyme
Catalysts for Efficient Dynamic Kinetic
Resolution of Alcohols at Ambient
Temperature
The combination of highly compatible
metal and enzyme catalysts allows the
fastest dynamic kinetic resolution of
alcohols ever reported. The use of ruthenium catalyst 1 a (or 1 b) and an immobi-
Mass Spectrometry
lized lipase results in a highly efficient
enantioselective synthesis of acetates in
excellent yields at room temperature
(see scheme).
Flying to new destinations: Instrument
modifications, which give three detection
areas (see scheme) in a two-channel
detection scheme, extend the achievable
duty cycle of a Hadamard transform timeof-flight mass spectrometer (HT-TOFMS)
to 100 % and effectively converts TOFMS
into a continuous detection technique.
Beyond the improved signal-to-noise
ratio, this advance gives an increase in the
data-acquisition rate leading to a higher
detection speed.
O. Trapp, J. R. Kimmel, O. K. Yoon,
I. A. Zuleta, F. M. Fernandez,
R. N. Zare*
6541 – 6544
Continuous Two-Channel Time-of-Flight
Mass Spectrometric Detection of
Electrosprayed Ions
Homogeneous Catalysis
The golden key: The use of N and N,O
ligands for gold(iii) complexes leads to
stable catalysts that facilitate an efficient
synthesis of tetrahydroisoquinolines with
substitution patterns difficult to access by
classic methods (see picture).
A. S. K. Hashmi,* J. P. Weyrauch,
M. Rudolph, E. Kurpejović
6545 – 6547
Gold Catalysis: The Benefits of N and
N,O Ligands
CC Coupling
M. RZssle, T. Werner, A. Baro, W. Frey,
6547 – 6549
J. Christoffers*
Formation of 1,4-Diketones by Aerobic
Oxidative CC Coupling of Styrene with
1,3-Dicarbonyl Compounds
Convenient and direct: 1,4-Dicarbonyl
compounds are readily obtained through
a one-pot cerium-catalyzed oxidative CC
Disproportionation of a metastable GaI
chloride solution and substitution with
phosphanides leads to a novel type of
metalloid Ga22 clusters ([Ga22(PtBu2)12],
see molecular structure, Ga: blue and
black, P: gray). The four previously discovered Ga22 structural isomers—which
in solid-state chemistry would be referred
to as different phases—reflect the diverse
bonding possibilities in gallium
modifications.
Element Modifications
J. Steiner, G. StZßer,
H. SchnZckel*
6549 – 6552
[Ga22(PtBu2)12]: Diversity in the Arrangement of 22 Gallium Atoms—A Unique
Case in the Field of Metalloid Clusters?
6402
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
coupling in the presence of oxygen and
subsequent fragmentation. The products
are suitable precursors for heterocycles.
www.angewandte.org
Angew. Chem. Int. Ed. 2004, 43, 6394 – 6403
Angewandte
Chemie
Spirocycles
A. de Meijere,* A. F. Khlebnikov,
S. I. Kozhushkov, K. Miyazawa, D. Frank,
P. R. Schreiner, B. C. Rinderspacher,
D. S. Yufit, J. A. K. Howard 6553 – 6557
Remarkably high specific rotations, even
at 589 nm, are exhibited by the enantiomerically pure s-[9]helicenes (M)-()- and
(P)-(þ)-[9]triangulanes (see scheme).
This significant power of rotation, which is
in very good agreement with calculated
values, must be attributed to the rigid
helical framework of s bonds in these
formally saturated hydrocarbons.
A Convergent Route to Enantiomerically
Pure Higher [n2]Triangulanedimethanol
Derivatives and [n]Triangulanes (n 7)
Communications labeled with this symbol have been judged by two referees as being “very important papers”.
Service
Keywords
6558
Authors
6559
Angewandte’s
Sister Journals
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Angew. Chem. Int. Ed. 2004, 43, 6394 – 6403
www.angewandte.org
6560 – 6561
6563
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
6403
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