Preparation of Cyclobutene Acetals and Tricyclic Oxetanes through Photochemical Tandem and Cascade Reactions.

We describe a photochemical reaction using two starting materials, a cyclopent-2-enone and an alkene, which are transformed in a controlled manner via the initial [2+2]-photocycloaddition adducts into cyclobutene aldehydes (conveniently trapped as stable acetals) or unprecedented angular tricyclic 4:4:4 oxetane-containing skeletons. These compounds are formed through tandem or triple cascade photochemical reaction processes, respectively. Small libraries of each compound class were prepared, thus suggesting that this photochemistry approach opens new opportunities for synthesis design and for widening molecular diversity.

ß-Cyclodextrin-Mediated Enantioselective Photochemical Electrocyclization of 1,3-Dihydro-2H-azepin-2-one.

The photochemical electrocyclization reaction of the title compound in the presence of ß-cyclodextrin was examined in different conditions. No enantioselectivity was observed in solution, but solid-state reactions of a 1:1 complex as a suspension or a thin film, followed by reduction, provided (1R,5R)-2-azabicyclo[3.2.0]heptan-3-one in isolated yields up to 79% and with ee values up to 45%.

The Multiple Facets of Iodine(III) Compounds in an Unprecedented Catalytic Auto-amination for Chiral Amine Synthesis.

Iodine(III) reagents are used in catalytic one-pot reactions, first as both oxidants and substrates, then as cross-coupling partners, to afford chiral polyfunctionalized amines. The strategy relies on an initial catalytic auto C(sp(3) )-H amination of the iodine(III) oxidant, which delivers an amine-derived iodine(I) product that is subsequently used in palladium-catalyzed cross-couplings to afford a variety of useful building blocks with high yields and excellent stereoselectivities. This study demonstrates the concept of self-amination of the hypervalent iodine reagents, which increases the value of the aryl moiety.

Tandem Catalytic C(sp(3) )-H Amination/Sila-Sonogashira-Hagihara Coupling Reactions with Iodine Reagents.

A new tandem C-N and C-C bond-forming reaction has been achieved through Rh(II) /Pd(0) catalysis. The sequence first involves an iodine(III) oxidant, then the in situ generated iodine(I) by-product is used as a coupling partner. The overall process demonstrates the synthetic value of iodoarenes produced in trivalent iodine reagent mediated oxidations.

Ruthenium-catalyzed C-C bond cleavage in lignin model substrates.

Ruthenium-triphos complexes exhibited unprecedented catalytic activity and selectivity in the redox-neutral C-C bond cleavage of the ß-O-4 lignin linkage of 1,3-dilignol model compounds. A mechanistic pathway involving a dehydrogenation-initiated retro-aldol reaction for the C-C bond cleavage was proposed in line with experimental data and DFT calculations.

Transition-metal-free synthesis of oxindoles by potassium tert-butoxide-promoted intramolecular α-arylation.

Potassium tert-butoxide-mediated intramolecular α-arylations of fluoro- and chloro-substituted anilides provide oxindoles in DMF at 80 °C. In this manner, diversely substituted products have been obtained in moderate to high yields.

Iron thiolate complexes: efficient catalysts for coupling alkenyl halides with alkyl Grignard reagents.

Ironing out the kinks: Efficient new catalytic systems based on iron thiolates are described for the iron-catalyzed cross-coupling of alkyl Grignard reagents with alkenyl halides. The reaction is highly chemo- and stereoselective. With this new procedure, the use of N-methylpyrrolidone as a co-solvent is no longer required.

Preparation of diastereomerically pure dilignol model compounds.

A gram-scale synthetic access to diastereomerically pure dilignol ß-O-4 type model compounds, which represent valuable candidates for studies of lignin cleavage and valorization, is described. Following a straightforward procedure both diastereoisomers of 1,3-dilignols can be prepared. In the key-step, tert-butyl aryloxy esters are used as enolate precursors for additions on aldehydes. After separation, the resulting erythro and threo ß-hydroxy esters are independently reduced to afford the target compounds in high yields.