If (iso?)setoclavine were readily obtainable, it certainly isn't watched yet, then it might not be too difficult to convert it to 9-methyl-LSD. The idea would be to convert the tertiary -OH to bromide or iodide, magnesium grignard and CO2, and conventional procedure from the acid. Is this worth a second thought anyone? Thanks.
Boron trihalide is a strong candidate (http://onlinelibrary.wiley.com/doi/10.1002/chin.199426072/abstract) as it does not add to double bonds and prefers tertiary alcohols. As a strong lewis acid, I think it's H+ specifically that ruins ergolines, but I'm not sure. Isomerization might also be a problem to some degree (http://pubs.rsc.org/en/Content/ArticleLanding/1971/J3/j39710003593)
http://pubs.acs.org/doi/abs/10.1021/ja01331a040 interestingly claims chloride gives higher yields of tertiary grignard reagent. How does the stereochem work on that, once its on there that CH3 wont be twisting around (I know it must be obvious but I haven't found a clear answer yet). Cyanide replacement is also an idea, but its almost sure to be sn1 cutting the yield in half, and then alkaline hydrolysis to the salt etc.
[edit]
Looking at this the molecule, I think it would readily isomerise, the desired product in low if any yield. Shift the double bond and the benzilic carbocation is more stable, and more sterically available to the BX3(OH)- .
Boron trihalide is a strong candidate (http://onlinelibrary.wiley.com/doi/10.1002/chin.199426072/abstract) as it does not add to double bonds and prefers tertiary alcohols. As a strong lewis acid, I think it's H+ specifically that ruins ergolines, but I'm not sure. Isomerization might also be a problem to some degree (http://pubs.rsc.org/en/Content/ArticleLanding/1971/J3/j39710003593)
http://pubs.acs.org/doi/abs/10.1021/ja01331a040 interestingly claims chloride gives higher yields of tertiary grignard reagent. How does the stereochem work on that, once its on there that CH3 wont be twisting around (I know it must be obvious but I haven't found a clear answer yet). Cyanide replacement is also an idea, but its almost sure to be sn1 cutting the yield in half, and then alkaline hydrolysis to the salt etc.
[edit]
Looking at this the molecule, I think it would readily isomerise, the desired product in low if any yield. Shift the double bond and the benzilic carbocation is more stable, and more sterically available to the BX3(OH)- .