Probing ergot alkaloid biosynthesis: Synthesis and feeding of a proposed intermediate along the biosynthetic pathway. A new amidomalonate for tryptophan elaboration

Alan P. Kozikowski, Makoto Okita, Motomasa Kobayashi, Heinz G. Floss

Research output: Contribution to journalArticlepeer-review

Abstract

The total synthesis of the diastereomeric amino acids 2 and their N-trideuteriomethyl analogues has been carried out. These compounds represent possible intermediates along the biosynthetic pathway from 4-(γ,γ dimethylallyl) tryptophan (1) to the ergot alkaloids (e.g., 3a). The synthetic scheme features the preparation of an (indolylvinyl)metallic reagent from 4-ethynylindole via a hydrostannylation/metal-metal exchange sequence, as well as the preparation of dimethyl [N-methyl-N-[(2,2,2-trichloroethoxy)carbonyl]amino]malonate, a new amidomalonate reagent for tryptophan elaboration. Incorporation experiments with Claviceps sp. SD58 followed by GC-MS analysis of the major alkaloid, elymoclavine, showed that neither diastereomer of 2-d3 is an ergot alkaloid precursor.

Original languageEnglish (US)
Pages (from-to)863-869
Number of pages7
JournalJournal of Organic Chemistry
Volume53
Issue number4
DOIs
StatePublished - Feb 1 1988

ASJC Scopus subject areas

  • Organic Chemistry

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