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Herein, the diversification of tricyclo[3.2.1.03,6]octane scaffolds to afford diverse bicyclic scaffolds is described. The strained tricyclooctanes are prepared in two steps featuring a blue light-mediated [2+2] cycloaddition. Strategies for the cleavage of this scaffold were then explored resulting in the selective syntheses of the bicyclo[3.1.1]heptane, bicyclo[3.2.1]octane, and bicyclo[3.2.0]heptane cores. These findings may guide future studies of C–C cleavage reactions in strained carbon frameworks and their application in complex molecule synthesis. [ABSTRACT FROM AUTHOR]

The pronounced beneficial effect of a precise amount of protic additive in an enantioselective Cu-catalysed Diels–Alder reaction is reported. This reaction, which employs a cyclic alkylidene β-ketoester as a dienophile, represents one of the first examples of a transformation where these extremely versatile, though highly unstable reaction partners participate effectively in catalytic asymmetric cycloaddition with a functionalised diene. The cycloadduct was used as an intermediate towards the synthesis of magellanine-type Lycopodium alkaloids featuring a Stille cross-coupling of a highly congested enol triflate and a unique Meinwald rearrangement/cyclopropanation sequence. [ABSTRACT FROM AUTHOR]

Substituted piperidines are emerging as important medicinally-active structural motifs. Here, we report highly stereoselective carbolithiation reactions of α-aryl piperidine enecarbamates that offer direct access to vicinally-substituted piperidine compounds. We have also demonstrated that the carbanion intermediates can be trapped with a carbon electrophile. [ABSTRACT FROM AUTHOR]

Methods that furnish enantioenriched products are crucial in modern organic synthesis. An underutilized strategy to arrive at enantioenriched products is to perform divergent reactions on racemic mixtures, where each enantiomer of the starting material reacts with a single chiral reagent to furnish two separable, non-enantiomeric products that are enantioenriched. Stereodivergent, regiodivergent and structurally divergent reactions on racemic mixtures are discussed in this tutorial review. [ABSTRACT FROM AUTHOR]

We report the modular preparation of dihydro-1,2,5-thiodiazole dioxide heterocycles starting from methyl ketones and primary amines. This one-pot, three-component coupling employs 2,3-dimethylimidazole-1-sulfonyl azide triflate as a coupling reagent and oxidant. The transformation is scalable and various ketones and amines can be used, yielding thiodiazole dioxide products in up to 89% yield. In addition, 15 N- and 13 C-labeling studies suggest a mechanism involving a 1,2-nitrogen migration. Together with the mechanistic studies, DFT calculations provide insight into the reaction pathway and set the stage for further exploration of the mechanistic nuances of reactions that use sulfamoyl azides. In combination with the demonstrated modularity of the approach reported herein, the derivatization of the thiodiazole dioxide products highlights the potential of this methodology to rapidly access diverse chemical structures., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The methoxime group has emerged as a versatile directing group for a variety of C-H functionalizations. Despite its importance as a powerful functional handle, conversion of methoximes to the parent ketone, which is often desired, usually requires harsh and functional group intolerant reaction conditions. Therefore, the application of methoximes and their subsequent conversion to the corresponding ketone in a late-stage context can be problematic. Here, we present an alternative set of conditions to achieve mild and functional group tolerant conversion of methoximes to the parent ketones using photoexcited nitroarenes. The utility of this methodology is showcased in its application in the total synthesis of cephanolide D. Furthermore, mechanistic insight into this transformation obtained using isotope labeling studies as well as the analysis of reaction byproducts is provided., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The synthesis of diverse N -fused heterocycles, including the pyrido[1,2- a ]indole scaffold, using an efficient pyrone remodeling strategy is described. The pyrido[1,2- a ]indole core was demonstrated to be a versatile scaffold that can be site-selectively functionalized. The utility of this novel annulation strategy was showcased in a concise formal synthesis of three fascaplysin congeners., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

A unified strategy for the synthesis of congeners of the prenylated indole alkaloids is presented. This strategy has yielded the first synthesis of the natural product (-)-17-hydroxy-citrinalin B as well as syntheses of (+)-stephacidin A and (+)-notoamide I. An enolate addition to an in situ generated isocyanate was utilized in forging a key bicyclo[2.2.2]diazaoctane moiety, and in this way connected the two structural classes of the prenylated indole alkaloids through synthesis.

Indolizinones are under-explored N-heterocycles that react with exquisite chemo- and stereoselectivity. An exploration of the fundamental reactivity of these azabicycles demonstrates the potential to relay stereochemical information from the ring-fusion to newly formed stereocenters on the bicyclic core. The indolizinone diene undergoes selective hydrogenation and readily participates in Diels-Alder cycloadditions as well as ene reactions. The vinylogous amide embedded in the five-membered ring is resistant to reaction when the diene is in place. However, removal of the diene allows for diastereoselective hydrogenation of, and 1,4-additions to, the vinylogous amide. These fundamental reactions with indolizinones have provided a structurally diverse array of products that hold promise in the context of natural product synthesis.

Hetero-cycloisomerization reactions of propargylic alcohol derivatives leading to indolizines have been demonstrated to proceed in the presence of water alone. This stands as a significant advance over the previous methods using Pt, Cu or Ag salts paired with ligands in organic solvents such as benzene, acetonitrile or methylene chloride.