Synthesis of brassinosteroids and relationship of structure to plant growth-promoting effects.

A number of brassinosteroids with and without hydroxyl groups or an alkyl substituent in their side chain were synthesized. The alkyl substituent at C-24 highly influenced the oxidation of the C-22 double bond with osmium tetroxide and, hence the ratio of the 22 beta,23 beta- and 22 alpha,23 alpha-glycolic isomers obtained. Two different bean bioassays used to compare the plant growth-promoting capabilities of these compounds and of brassinolide and its three side chain 22,23-cis-glycolic isomers showed that brassinolide was the most active. The next most active brassinosteroids were generally those with 22 alpha-OH, 23 alpha-OH orientation and a beta-methyl or alpha-ethyl substituent at C-24. Similarly, of the synthetic precursor tetrahydroxy ketones of the brassinosteroids, those with 22 alpha-OH, 23 alpha-OH orientation (like brassinolide) and an alkyl group at C-24 were also the most active in both bioassays. The results indicate stringent structural features are required for a steroid to induce brassin activity. The structural requirements are: a trans A/B ring system (5alpha-hydrogen), a 6-ketone or a 7-oxa-6-ketone system in ring B, cis alpha-oriented hydroxyl groups at C-2 and C-3, cis hydroxy groups at C-22 and C-23 as well as a methyl or ethyl substituent at C-24.