No hurdle is too high : The regioselectivity and stereoselectivity of the halohydroxylation of non‐activated allenes are controlled by a remote sulfinyl group through anchimeric assistance (see scheme). The resulting halohydrines are excellent chiral targets for the preparation of optically pure propargylic alcohols and Baylis–Hillman‐type products.
Ester‐way to heaven : Unexpected formation of bicyclo[3.1.0]hexene 4 was the main focus of combined experimental and theoretical studies on the Au‐catalyzed cycloisomerization of branched dienyne 1 (see scheme), which provided better understanding of the mechanistic details governing the cyclization of enynes bearing a propargylic ester group.
Easy and direct : Regioselective Mizoroki–Heck‐coupling reactions using heteroaromatic tosylates as electrophiles were achieved, thus providing direct and easy access to highly functionalized α‐heteroarylvinyl amides and ethers.
Reaction rates from polarized spectroscopy : A new method based on ultrafast pump–probe polarization spectroscopy enables the measurement of the ground‐ and excited‐state reaction rates for self‐exchange processes. The technique was used to study double hydrogen transfer in porphycene and its derivatives (see figure).
Nonlinearities in atomic vapors allow the production of “entangled images”—beams of light whose transverse light distributions exhibit localized correlations in their unavoidable quantum fluctuations (see picture). These spatially entangled beams may prove useful to reduce the noise in absorption imaging and beam positioning below the quantum noise level, as well as for quantum information applications.
Buckle up! The dimerization of small fluorescent guests is strongly enhanced in presence of a cyclodextrin host. The host cavity acts like a belt to assist the self‐assembly of guests (see picture). Small variations in the guest structure have significant influence on the stability and geometry of the aggregates.
Photoproduct signature: Irradiation of solid hydrogen near 3 K containing NO with vacuum‐UV light from synchrotron radiation yields new infrared absorption lines at 1241.7, 1063.6 and 726.2 cm?1 (see figure). These new lines are assigned to vibrational modes of t‐HNOH. This photoproduct is formed from electronically excited NO reacting with neighboring hydrogen in the solid sample.
Aryl–alkyl cross‐coupling products are obtained by the iron‐catalyzed oxidative heterocoupling of organozinc reagents under mild conditions. This novel reaction pathway is versatile, allowing for the use of primary and secondary aliphatic diorganozinc reagents as coupling partners as well as tolerating functionalized aryl‐ and alkylzinc reagents.
Seven in one blow : The efficient formation of mixed disulfides on the thiol‐rich fusion protein A followed by subsequent intein cleavage gave the fragment B with all seven cysteines protected against oxidation. The native chemical ligation of B with synthetic glycopeptide thioesters provides glycoproteins.
2009: A boraanthracene odyssey : General routes to boraanthracene derivatives—long proposed, but never observed—are disclosed, along with the structural and photophysical properties of these compounds and their remarkable reactivity towards oxygen.
A simple but effective copper‐catalyzed borylation of aryl halides, including electron‐rich and sterically hindered aryl bromides, with alkoxy diboron reagents occurs under mild conditions (see scheme). Preliminary DFT studies of the mechanism suggest that σ‐bond metathesis between a copper–boryl intermediate and the aryl halide generates the aryl boronate product.
