Agro clavine

The structures of setoclavine (LXIX), isosetoclavine (LXX), penni-clavine (LXXI), and isopenniclavine (LXXII) were, for the major part, obtained from the oxidative formation of these alkaloids from agro-clavine (LX) and elymoclavine (LIX). 

A general synthetic route from elymoclavine (56 A ) to a variety of substituted A -ergolenes, by displacement reactions on the related allylic chloride, has been developed. A rather more exciting contribution is the partial synthesis of agro-clavine (63) from chanoclavine-I (61) and isochanoclavine-I (62) (Scheme 9) the... 

Ikan, R. etal. 19(38. The presence of agro-clavine in Cuscuta monogyna seeds Israeli Journal of Chemistry 6(1) 65—67. 

The synthesis of dimethylallyltryptophan (132) by a crude extract of Claviceps purpurea from tryptophan and dimethylallyl pyrophosphate recorded earlier has been reported again recently. In addition to (132), the formation of (133) was observed. (The latter compound, with unspecified stereochemistry around the double bond, has also been isolated from a C. purpurea culture ). It was found further that both (132) and (133) could act as precursors for lysergic acid amides in C. paspali cultures. Both (133) and its (Z)-isomer have been found to act as precursors for elymoclavine (137) but not chanoclavine-I (138) or agro-clavine (136), which are considered to be normal intermediates in elymoclavine biosynthesis.It may be concluded, however, from the combined evidence, that elymoclavine, lysergic acid, and related compounds may normally be formed along an alternative pathway via these allylic hydroxy-compounds. 

Key intermediates are the tricyclic chanoclavine I and the tetracyclic agro-clavine. cis-trans-Isomerizations take place in the transformation of 4-dimethyl-allyltryptophan to chanoclavine (cf. the position of the labelled methyl... 

---