[curiouscat]

In natutre, Cytochrome P450 systems are said to perform the following transformation of adding an -OH group to a terpene:

   


What could be possible organic synthetic options to do the same? Any reagents of choice to to this which would retain the sterochemistry?

[discodermolide]

Not quite terpenes, but have a look here. DOI: 10.1021/acs.oprd.5b00282

[curiouscat]

Not quite terpenes, but have a look here. DOI: 10.1021/acs.oprd.5b00282

Very interesting. Will read.

Would none of the standard hydroxylating agents in your arsenal do this job?

[orgopete]

I cannot think of any reagents that could carry out this transformation in a specific way. I can think of kinds of reactions that might attack the trisubstituted double bond to functionalize the methyl group, but don't lead to your product, for example, singlet oxygen formation of perepoxide and reduction. It would give the terminal alkenyl alcohol which would require further transformation. Selenium dioxide would be similar, but favor reaction at the methylene.

Given how challenging the alternatives are, you might try allylic halogenation, substitution, and separation or ozone, Wittig (Emmons), and reduction. Are there any microbes or microbial preparations that can carry out the P450 oxidation?

[curiouscat]

I cannot think of any reagents that could carry out this transformation in a specific way.

There's a patent that says this:

"The further processing [adding the -OH group at the required position] may be carried out by any means known to the skilled person, such as use of an appropriate cytochrome P450 enzyme, or chemical reactions such as alkaline metalation, borylation and oxidation, to yield the correct cis alcohols."

[curiouscat]

Are there any microbes or microbial preparations that can carry out the P450 oxidation?

Yes, that's the Plan B. But if I can do it with a synthetic reagent I'd prefer that.