Total Synthesis of (−)-Clavicipitic Acid via γ,γ-Dimethylallyltryptophan (DMAT) and Chemoselective C–H Hydroxylation | Zendy

Francesca Bartoccini | Zendy; Silvia Venturi | Zendy; Michele Retini | Zendy; Michele Mari | Zendy; Giovanni Piersanti | Zendy

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Total Synthesis of (−)-Clavicipitic Acid via γ,γ-Dimethylallyltryptophan (DMAT) and Chemoselective C–H Hydroxylation

Author(s) -

Francesca Bartoccini,

Silvia Venturi,

Michele Retini,

Michele Mari,

Giovanni Piersanti

Publication year - 2019

Publication title -

the journal of organic chemistry

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 1.2

H-Index - 228

eISSN - 1520-6904

pISSN - 0022-3263

DOI - 10.1021/acs.joc.9b00879

Subject(s) - chemistry , hydroxylation , indole test , aziridine , prenylation , boronic acid , stereochemistry , total synthesis , brønsted–lowry acid–base theory , organic chemistry , ring (chemistry) , catalysis , enzyme

The first total synthesis of natural (-)-clavicipitic acid from γ,γ-dimethylallyltryptophan (DMAT), its biosynthetic precursor, is described. This is done by regio- and chemoselective, remote, nondirected C(sp 3 )-H hydroxylation followed by aminocyclization. This study also features regio- and chemoselective Pd(0)-catalyzed linear prenylation at C4 of l-tryptophan boronic pinacol ester derivate, the latter obtained by a Lewis acid-promoted aziridine amino acid ring opening with 4-boronated indole. In addition, these results support the hypothesis that oxidative cyclization between amino acid nitrogen and the prenyl chain during clavicipitic acid biosynthesis can occur through the transient hydroxylated intermediate.

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