Dithioles - A Universal Scaffold for Organic Synthesis (Important Papers)

As there is no comprehensive reviews anywhere which showcase the versatility of these reagents, I decided to spill the beans on some of the best chemistry out there.

In this video, I share what is arguably the most versatile building block in organic synthesis - the dithiole. It's like a Corey dithiane but way easier to manipulate - need to make a carbonyl? Simply use Ag2O. Want a CH2? Use Raney nickel. Mild bases can be used once you start oxidizing the dithiole to the sulfoxide(s) and sulfone forms, meaning that they can readily be alkylated or coupled with various electrophiles. You can also make them react as carbenes (from the 2-chloro-sulfone, for example)!


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Important Papers covers various chemical reactions, mechanisms, and research papers in the field of organic chemistry, providing examples and explanations for each research paper.

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References:
Huge BDT review (1985; featuring some stuff which wasn't discussed here) - https://doi.org/10.1080/0196177850808...
Dioxygenase ref 1 - https://pubs.acs.org/doi/10.1021/ja00...
Dioxygenase ref 2 - https://doi.org/10.1016/j.tet.2003.10...
dithiole oxidation to sulfoxide, sulfone, and carbene chem - https://doi.org/10.1016/S0040-4020(01...
Dithiole monosulfoxide chlorination - https://doi.org/10.1055/s-1985-31261
Lithiation of dithiole with trapping by aldehydes and ketones - https://doi.org/10.1016/j.tet.2003.10... (the dioxygenase paper)
Another aldehyde/ketone paper which I don't have the DOI of - Brown, Charles Allan; Chapa, O.; Yamaichi, A.[Heterocycles, 1982, vol. 18, p. 187 - 189]
Fluorination of the dithiole bis-sulfone with selectfluor - https://doi.org/10.1002/anie.200906866
N-parameters of bis-sulfone and fluoro bis-sulfone (they dinked up the figure and had to submit a correction btw) - https://doi.org/10.1002/anie.201605616
1,2- and 1,4- substitution of the fluoro bis sulfone - https://doi.org/10.1002/anie.200906866
Eeros BDT-BF4 - https://doi.org/10.1002/047084289X.rb027
Tributyltin hydride on the BDT ether and amines - https://pubs.acs.org/doi/10.1021/jo00...
Adding in the mono sulfoxide into nitroarenes - https://doi.org/10.1080/1042650930803...
imine scandium triflate cyclization - https://pubs.acs.org/doi/10.1021/ol02...
chloro bis-methyl acetal dithiafulvalene synthesis from dithiol - https://doi.org/10.1002/jhet.5570310676
intramolecular domino cyclization of dithiafulvalene (aka EAS reaction) - https://doi.org/10.1021/jo00304a021
^paper also discusses the chemoselective transformations from slide 30
indole functionalization of DMBDT, difluoroether synthesis, radiofluorination, etc - https://doi.org/10.1002/chem.202202862
My PhD thesis "New Fluorination Strategies and Reagents" -
https://summit.sfu.ca/item/37816
Trityl BF4 synthesis - https:doi.org/10.1055/s-1972-21914 (the other ways using carboxylic acid anhydrides suffer from purification issues - it is easier to do it this way if you don't hate yourself)
Eeros Trityl BF4 Review - https://doi.org/10.1002/047084289X.rt...
TTF/DTF article 1 - https://link.springer.com/article/10....
TTF/DTF article 2 - https://doi.org/10.1002/chem.201802744

Dear materials scientists, please make 1 product with dithiafulvalenes or tetrathiafulvalenes by 2030, otherwise the organic chemists will think you are clowning

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