Ketenimines as Intermediates To Access Difluoromethoxylated Scaffolds

We report herein the in situ generation of difluoromethoxylated ketenimines. This novel intermediate is readily obtained from the corresponding oxime through a Beckmann rearrangement. The reactivity potential of this species is demonstrated as it easily undergoes addition of various nucleophiles, with a great modularity of the starting oxime. The broad applicability of this transformation leads to a chemical library of original molecules bearing −OCHF2, an Emergent Fluorinated Group (EFG)

In Situ Generated Fluorinated Iminium Salts for Difluoromethylation and Difluoroacetylation

The use of TFEDMA, a fluoroalkyl amino reagent, for the difluoromethylation and difluoroacylation of arenes, heteroarenes, and C–H acidic compounds is reported. This approach allows for an efficient access to difluoromethylated products of high added value in good to excellent yields and with scale-up possibilities

Chromium-Templated Benzannulation of (η⁵-Cyclohexadienyl)Mn(CO)₃-Methoxy-Cr(CO)₅ Carbenes

Pentacarbonyl­{methoxy-[1-(η⁵-4-methoxy-6-phenylcyclohexadienyl)­tricarbonylmanganese]­carbene}­chromium (<b>5</b>) accessible from (η⁵-1-bromo-4-methoxy-6-phenylcyclohexadienyl)­tricarbonylmanganese (<b>4</b>) and Cr­(CO)₆ undergoes a chromium-templated benzannulation with 3-hexyne to give monometallic Cr complex <b>12</b> in 60% yield. The key feature of this reaction is the participation of a conjugated double bond of the η⁵-cyclohexadienyl-Mn moiety in the [3+2+1] benzannulation reaction. The X-ray structure of complex <b>12</b> reveals a <i>syn</i> position of the phenyl group with respect to the Cr tripod, supporting the participation of the Mn moiety in the benzannulation process

Stereoselectivity Switch in the Trapping of Polar Organometallics with Andersen’s ReagentAccess to Highly Stereoenriched Transformable Biphenyls

The trapping of racemic polar carbometallic species with (−)-menthyl (<i>S</i>_S)-<i>p</i>-toluenesulfinate (Andersen’s reagent) typically proceeds with a very low level of resolution. In this paper, we describe a strategy that allows access to highly atropo-enriched and functionalizable biphenyls by means of Andersen’s reagent under kinetic resolution conditions. In particular, useful enantiopure 2-iodobiphenyls could be obtained and were employed in a challenging hypervalent iodine-catalyzed oxidation reaction

Stereoselectivity Switch in the Trapping of Polar Organometallics with Andersen’s ReagentAccess to Highly Stereoenriched Transformable Biphenyls

The trapping of racemic polar carbometallic species with (−)-menthyl (<i>S</i>_S)-<i>p</i>-toluenesulfinate (Andersen’s reagent) typically proceeds with a very low level of resolution. In this paper, we describe a strategy that allows access to highly atropo-enriched and functionalizable biphenyls by means of Andersen’s reagent under kinetic resolution conditions. In particular, useful enantiopure 2-iodobiphenyls could be obtained and were employed in a challenging hypervalent iodine-catalyzed oxidation reaction