The synthesis of 3-amino-3-methylbicyclo[3.3.1]nonanes: Endo-selectivity in the Ritter reaction of 1,3,5,7α-tetramethylbicyclo[3.3.1]nonan-3-ol

Cooperative activation of cyclobutanones and olefins leads to bridged ring systems by a catalytic [4 + 2] coupling

“…1c , Murakami/Ito) 31 did not provide any of the desired bicycle (entry 1, Table 1 ). However, [Rh(COD)Cl] 2 was found to be a promising precatalyst and the desired bridged bicycle (3-azabicyclo[3,3,1]nonanone) 2a 43 – 47 was obtained albeit in low yields (entry 2). The solvent effect was next evaluated and 1,4-dioxane proved to be the best solvent (entries 3–5).…”

Total Synthesis of the Chlorine‐Containing Hapalindoles K, A, and G

“…Application of a Ritter reaction to 14 using TMSCN as a nitrogen source provided formamide 15b as a single diastereomer. [16] Formation of an allylic cation and axial approach of the nucleophile again rationalizes the diastereoselection, which was further confirmed by the observation of a NOESY crosspeak as shown in Scheme 4. A second possible source of stereocontrol is the close proximity of the equatorial position to C2 of the indole ring, resulting in an unfavorable steric interaction.…”

Cover Picture: Methylidene Rare‐Earth‐Metal Complex Mediated Transformations of CN, NN and NH Bonds: New Routes to Imido Rare‐Earth‐Metal Clusters (Chem. Eur. J. 24/2013)

“…The coupling constants associated with the chloro‐substituted axial methine ( J =9 and 5.4 Hz) support the assignment of the acetate to an axial position. Application of a Ritter reaction to 14 using TMSCN as a nitrogen source provided formamide 15 b as a single diastereomer 16. The formation of an allylic cation and an axial approach of the nucleophile again rationalize the diastereoselectivity, which was further confirmed by the observation of a NOESY cross‐peak (in Scheme ).…”