First stereospecific total synthesis of (−)-affinisine oxindole as well as facile entry into the C(7)-diastereomeric chitosenine stereochemistry. Issue 23 (3rd June 2015)

• Record Type: Journal Article
• Authors: Fonseca, German O.; Wang, Zhi-Jian; Namjoshi, Ojas A.; Deschamps, Jeffrey R.; Cook, James M.
• Is Part Of: Tetrahedron letters. Volume 56:Issue 23(2015)
• Page Start: 3052
• Page End: 3056
• Publication Date: 2015-06-03
• Subjects: Affinisine oxindole -- Oxindoles -- Oxindole-rearrangement -- Palladium-catalyzed cross coupling -- Tetrahydro-β-carbolines; Chemistry, Organic -- Periodicals; 547.005
• DOI: 10.1016/j.tetlet.2014.11.036
• Languages: English
• ISSNs: 0040-4039

Abstract

Graphical abstract: The first synthesis of (−)-affinisine oxindole was completed in an enantiospecific fashion from commercially availabled -(+)-tryptophan in 10% overall yield. The asymmetric Pictet–Spengler reaction, diastereospecific oxidative-rearrangement of a tetrahydro-β-carboline, and stereospecific enolate-mediated palladium-catalyzed cross coupling process were key steps in the sequence. This represents the first example of a total synthesis via stereospecific entry into either the alstonisine related or epimeric chitosenine related oxindole stereochemistry depending on the presence or absence of an N b -benzyl protecting group. Abstract: The first synthesis of (−)-affinisine oxindole was completed in an enantiospecific fashion from commercially availabled -(+)-tryptophan in 10% overall yield. The asymmetric Pictet–Spengler reaction, diastereospecific oxidative-rearrangement of a tetrahydro-β-carboline, and stereospecific enolate-mediated palladium-catalyzed cross coupling process were key steps in the sequence. This represents the first example of a total synthesis via stereospecific entry into either the alstonisine related or epimeric chitosenine related oxindole stereochemistry depending on the presence or absence of an N b -benzyl protecting group.