Asymmetric Total Synthesis of (+)-Epiibogamine Enabled by Three-Component Domino Michael/Michael/Mannich Annulation of -Sulfinyl Metallosilylenamines.

The iboga alkaloids are promising antiaddictive and neuroregeneration candidates for medical treatment. There is a lack of studies for C20-epi iboga alkaloids due to the synthetic difficulties. Herein we report the shortest total synthesis of (+)-epiibogamine in seven steps from trimethyl orthobutyrate.

Diastereoselective Hydroxylation of --Butanesulfinyl Imines with 2-(Phenylsulfonyl)-3-phenyloxaziridine (Davis Oxaziridine).

The diastereoselective α-hydroxylation of --butanesulfinyl metallodienenamine and metalloenamines with Davis oxaziridine affords α-hydroxy -sulfinyl imines with 50-88% yield and up to 98:2 diastereomeric ratio. Dramatic changes in diastereoselectivity and stereoselectivity were observed by choice of metal bases. The mechanistic understanding for the switch in diastereoselectivity was assisted by DFT computational modeling, which suggests the facial approach is governed by aza-enolate geometry.

Oxidative addition of activated aryl-carboxylates to Pd(0): divergent reactivity dependant on temperature and structure.

With the exception of activated sulfonate esters, oxidative addition of Ar-O bonds to Pd(0) complexes is extremely rare. This has led to a general perception that Pd-catalyzed cross-coupling is not feasible with O-based electrophiles such as aryl esters. We report that pyrone and coumarin esters do undergo oxidative addition to Pd(PCy3)2, with Pd insertion into either the acyl-O or Ar-O bond.

Imidazolyl-phenyl (IMP) anions: a modular structure for tuning solubility and coordinating ability.

The effect of counteranion upon a cation's solution-phase reactivity depends on a subtle interplay of weak interactions. Although these effects are widely appreciated in synthesis and catalysis, probing and controlling anion-cation interactions remains a significant challenge. Here we report the synthesis, characterisation and reactivity of the IMP anions, a family of anions with a coordinating ability that can be tuned for a given application.