Formal One Carbon Deletion of Indoline Hemiaminals under Tautomeric Control to Access 2-Aminobenzyl Compounds.

Unprecedented tert-BuOK-mediated one carbon deletion of indoline hemiaminals has been achieved. This novel protocol provides an efficient synthetic tool for the construction of 2-aminobenzyl compounds with high chemoselectivity. In addition, functionalized 2-aminobenzyl compounds are difficult to make, for which few limited means of access currently exist. The key to success is the use of in situ generated Heyns rearrangement products (α-amino carbonyl compounds) as precursors for formal one carbon deletion.

On Demand Synthesis of C3-N1' Bisindoles by a Formal Umpolung Strategy: First Total Synthesis of (±)-Rivularin A.

In this work, a straightforward synthesis of C3-N1' bisindolines is achieved by a formal umpolung strategy. The protocols were tolerant of a wide variety of substituents on the indole and indoline ring. In addition, the C3-N1' bisindolines could be converted to C3-N1' indole-indolines and C3-N1'-bisindoles. Also, we have successfully synthesized (±)-rivularin A through a biomimetic late-stage tribromination as a key step.

One-Pot Synthesis of Core Structure of Shewanelline C Using an Azidoindoline.

The unprecedented synthesis of the indolines bearing N3-quinazolin-2,4-dione moiety using an AZIN is reported. The concise synthesis features the tandem Staudinger/chemo-selective aza-Wittig/cyclization sequence of AZINs with isatoic anhydride by a one-pot protocol.