OC tidbits #6

Nicolaou et al. (JACS)

Nicolaou et al. does some medicinal chemistry on prostaglandins. Take a look at this Bobbit‘s salt protocol for deprotection/oxidation combo. It seems like they overload the reaction, compared to the original paper, which used 3 equivalents of the oxidant, but who cares if it works?

Bobbit_Nicolaou

Moragas et al (ACIE)

Unprecedented (c) sigmatropic rearrangement of aziridines into sulfoximines.

Stockman_rearrangement

And De Kimpe’s rearrangement for comparison.

deKimpe_rearrangement

Li et al (ACIE)

I’m not sure I would buy the proposed mechanism for the conversion below. The authors skip ‘−H2‘ step and get away with it by simply writing “the imine intermediate 44 […] underwent tautomerization and a key decarboxylation to generate 45 with higher oxidation state.” Something else is clearly happening under that −CO2 arrow and it’s not mere tautomerization.

Hamigerans-proposed-numbers

Wappes et al (ACIE)

So similar, yet so different halogens. I guess, NaF won’t give anything useful under these conditions.

halogens-NHTs

 

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Author: Slava Bernat

I did my PhD in medicinal chemistry/chemical biology of G protein-coupled receptors and then explored some chemical biology of non-coding RNA as a postdoc. Currently I'm working in a small biotech company in San-Francisco Bay area as a research chemist. I'm writing about science, which catches my attention in rss feed reader and some random thoughts or tutorials.

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