An efficient aerobic linear allylic C—H amination reaction (LAA) is reported under Pd(II)/bis-sulfoxide/Brønsted base catalysis. The reaction operates under preparative, operationally simple conditions (1 equiv. olefin, 1 atm. O2 or air), with reduced Pd(II)/bis-sulfoxide catalyst loadings while providing higher turnovers and product yields than systems employing stoichiometric benzoquinone (BQ) as the terminal oxidant. Palladium(II)/benzoquinone π-acidic interactions have been invoked in various catalytic processes and are often considered beneficial in promoting reductive functionalizations. When such electrophilic activation for functionalization is not needed, however, benzoquinone at high concentrations may compete with crucial ligand (bis-sulfoxide) binding and inhibit catalysis. Kinetic studies reveal an inverse relationship between the reaction rate and the concentration of BQ, suggesting that benzoquinone is acting as a ligand for Pd(II) which results in an inhibitory effect on catalysis.

Chiral gold­(I) catalysts have been designed based on a modified JohnPhos ligand with a distal C 2-2,5-diarylpyrrolidine that creates a tight binding cavity. The C 2-chiral element is close to where the C–C bond formation takes place in cyclizations of 1,6-enynes. These chiral mononuclear catalysts have been applied for the enantioselective 5-exo-dig and 6-endo-dig cyclization of different 1,6-enynes as well as in the first enantioselective total synthesis of three members of the carexane family of natural products. Opposite enantioselectivities have been achieved in seemingly analogous reactions of 1,6-enynes, which result from different chiral folding of the substrates based on attractive aryl–aryl interactions.

Abstract1,6‐Enynes bearing OR groups at the propargyl position generate α,β‐unsaturated gold(I)‐carbenes/ gold(I) stabilized allyl cations that can be trapped by alkenes to form cyclopropanes or 1,3‐diketones to give products of α‐alkylation. The best migrating group is p‐nitrophenyl ether, which leads to the corresponding products without racemization. Thus, an improved formal synthesis of (+)‐schisanwilsonene A has been accomplished. The different competitive reaction pathways have been delineated computationally.

Gold(I)‐catalyzed cycloisomerizations of 1,n‐enynes proceed through electrophilic intermediates that can be trapped intra‐ or intermolecularly by a variety of hetero‐ and carbon nucleophiles to form complex skeletons in a single step. This review covers the efforts of our group towards the development of new reactions that have been successfully applied in the total synthesis of several natural terpenoids and related carbocyclic structures, as well as for the ready access to challenging linear acenes.

The synthesis of a new C 3v‐symmetric crushed fullerene C60H24 (5) has been accomplished in three steps from truxene through sixfold palladium‐catalyzed intramolecular arylation of a syn‐trialkylated truxene precursor. Laser irradiation of 5 induces cyclodehydrogenation processes that result in the formation of C60, as detected by LDI‐MS.

This work is dedicated to David Milstein in honor of his 70 th birthday.The deaminativeh ydrogenation of nitriles towards alcohols is au seful reaction to transform nitriles into alcohols with NH 3 as the sole byproduct. Using the simplea nd robust RuHCl-(CO)(PPh 3 ) 3 complexa sacatalyst, at low H 2 pressures as eries of aliphatic and aromaticn itriles could be transformed into the correspondinga lcohols. Suitable solvent systemsf or theser eactions were 1,4-dioxane/water and EtOH/water mixtures.I n most cases, the selectivity for the alcohols wase xcellent, and the corresponding amines were formed only in trace amounts.

We dedicate this paper to the memory of Friedhelm Balkenhohl Abstract: An ew approach for the efficient and highly selective synthesis of 1,2-amino alcohols by direct reductiveh ydrolysis of N-formyl-protected a-aminon itriles is reported. The commercially available RuHCl(CO)(PPh 3 ) 3 complex was found to be as uitable catalyst for this operationally simple protocol, in whichn os toichiometric amountso fu ndesired metal waste are generated. The deaminative hydrogenation is performed at 55 bar of H 2 ,u sing a6:1 mixture of 1,4-dioxane/water as solvent. In addition, hydroxymethyl alcohols were prepared from cyanoketones under very similarc onditions.

The past years have seen waves of societal change worldwide and increasing recognition that the sea of humanity consists of individual droplets-each of value and with valid perspectives.T he scientific community has realized that strength lies exactly in this diversity,a nd that mutual respect and open communication are essential for progress.A lthough many face-to-face interactions have not been possible this past year, dialogue,n etworks,a nd collaborations remain vital for researchers.During this time,t he editorial team-with the guidance of the German Chemical Society (GDCh) and the journals International Advisory Board [1] and Scientific Advisory Committee [2] -has considered how Angewandte Chemie can continue to support scientists and contribute to international scientific discourse. Angewandte Chemie,the flagship journal of the GDCh, is widely read. With such reach comes an opportunity and aresponsibility to engage with the challenges faced by the community.