[reaction: see text] The palladium-catalyzed coupling reaction of potassium alkenyltrifluoroborates with aryl or alkenyl halides or triflates proceeds readily with good yields. The trifluoroborates are air- and moisture-stable solids that can be stored indefinitely. The cross-coupling can be effected using PdCl(2)(dppf).CH(2)Cl(2) as the catalyst in n-PrOH in the presence of Et(3)N. A variety of functional groups are tolerated.

Working in tandem: Highly functionalized pyrroles and pyrazoles can be synthesized from a domino Cu‐catalyzed CN coupling/hydroamidation sequence. The scope and the generality of the method is noteworthy as a wide variety of substituents, either in the alkene or alkyne counterparts, are well tolerated.

A general and efficient method for the rhodium-catalyzed enantioselective catalytic conjugate addition of organoboronic acids to alpha,beta-unsaturated sulfones is described. The success of the process relies on the use of alpha,beta-unsaturated 2-pyridyl sulfones as key metal-coordinating substrates; typical sulfones such as vinyl phenyl sulfones are inert under the reaction conditions. Among a variety of chiral ligands, Chiraphos provided the best asymmetric induction. This rhodium [Rh(acac)(C2H4)2]/Chiraphos catalyst system has a broad scope, being applicable to the addition of both aryl and alkenyl boronic acids to cis and trans alpha,beta-unsaturated 2-pyridyl sulfones. In most cases, especially in the addition of aryl boronic acids, the reactions take place cleanly and with high enantioselectivity, affording chiral beta-substituted 2-pyridyl sulfones in good yields and enantioselectivities (70-92% ee). The sense and magnitude of this enantioselectivity have been studied by DFT theoretical calculations of the aryl-rhodium insertion step. These calculations strongly support the formation of a five-membered pyridyl-rhodium chelated species as the most stable complex after the insertion into the C=C bond. These highly enantioenriched chiral sulfones are very appealing building blocks in enantioselective synthesis. For instance, the straightforward elimination of the 2-pyridylsulfonyl group by either Julia-Kociensky olefination or alkylation/desulfonylation sequences provides a variety of functionalized chiral compounds, such as allylic substituted alkenes or beta-substituted ketones and esters.

A modular route to highly substituted pyrroles has been developed. This transformation consists of two sequential copper-catalyzed vinylations of bis-Boc-hydrazine followed by thermal rearrangement/cyclization. A wide variety of functionalized pyrroles can be prepared in a selective manner from simple and easily accessible precursors. [reaction: see text]

Both cyclic and acyclic silyl dienol ethers participate efficiently in the asymmetric vinylogous Mannich reaction of N-2-thienylsulfonylimines catalyzed by copper(I) complexes of Fesulphos ligands. This procedure displays wide imine and nucleophile versatility, high enantiocontrol, and complete gamma-regioselectivity in most cases examined. The mild sulfonamide deprotection allows the resulting products to be readily transformed into optically active delta-lactams or 5-hydroxy-2-piperidone derivatives.

A wide variety of 1,6-enynes and 1,7-enynes incorporating gamma-oxygenated-alpha,beta-unsaturated phenylsulfone moieties have readily been prepared by piperidine-promoted condensation of the corresponding alkynyl aldehyde with phenylsulfonyl-(p-tolylsulfinyl)methane and further protection of the hydroxyl group. Despite the enduring claim concerning the unsuitability of electronically deficient olefins in Pauson-Khand reactions, we report that these 1-sulfonylated enynes are excellent substrates in intramolecular Pauson-Khand reactions under both thermal and amine N-oxide-promoted conditions. Moreover, in contrast with the usual exo-selective Pauson-Khand cyclization of allylic substituted enynes, the reactions of these 1-sulfonylated-3-oxygenated enynes occur with a moderate or high endo selectivity. The evaluation of the chemical and stereochemical scope of the process in comparison with the Pauson-Khand cyclization of non-sulfonylated enynes, its application to the stereoselective preparation of optically pure C6-substituted bicyclo[3.3.0]oct-1-en-3-ones, and the interpretation of the stereochemical outcome are also discussed.

[reaction: see text] The molybdenum-mediated Pauson-Khand reaction promoted by Mo(CO)3(DMF)3 takes place under very mild conditions in the absence of any promoter. High yields in Pauson-Khand adducts are obtained in the cyclization of a wide variety of functionalized 1,6- and 1,7-enynes. Enynes bearing electron withdrawing groups at the alkene terminus are particularly good substrates.

Eins nach dem anderen: Hoch funktionalisierte Pyrrole und Pyrazole wurden mit einer Dominosequenz aus kupferkatalysierter C‐N‐Kupplung und Hydroamidierung synthetisiert. Die Anwendungsbreite der Methode ist beachtlich: Doppel‐ wie Dreifachbindung können verschiedenartige Substituenten tragen.