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Coupling of α-carboxyl sp3-carbons with aryl halides #84

Closed connorcoley closed 3 years ago

connorcoley commented 3 years ago

Substrate scopes (Figure 3 and 4A) from https://science.sciencemag.org/content/345/6195/437

Files attached. Lots of manually copying analytical/outcome data from the SI, unfortunately, in photoredox_data_analytical.csv Archive.zip

brilee commented 3 years ago

Comments:

connorcoley commented 3 years ago
  • Ir should be in the [3+] oxidation state, not [5+].

As-written with the dative bonds, I think Ir should be [Ir+] (definitely not [Ir+5] though, good catch. Does Ir+ seem reasonable to you? I had a back and forth with @michaelmaser about how to represent the complex and settled on CC(C)(C)C1=CC2=N(->[Ir+]34(<-N5=CC(C(F)(F)F)=CC=C5C5=C(F)C=C(F)C=C53)(<-N3=CC(C(F)(F)F)=CC=C3C3=C(F)C=C(F)C=C34)<-N3=C2C=C(C(C)(C)C)C=C3)C=C1.F[P-](F)(F)(F)(F)F

  • I take it that the C-H activation example wasn't digitized, just the arene and amide scopes?

Correct

  • For the 3x ether extractions, I noticed the workup type is "ADDITION"; shouldn't it be EXTRACTION?

The convention for workup steps that the proto recommends would be having multiple additions followed by an extraction step. But this is a recommendation I think I made, so we can certainly change it if there is good reason to. However, my default interpretation of an extraction step is that keep_phase is kept and everything else is discarded.

  • I double-checked to see if there was any wavelength information; seems like that is kind of important for a paper on photocatalysis... didn't see any, though.

Agreed - it's probably 460 nm, but better not to guess and leave it as "blue"

(Note: we should be blocked by https://github.com/open-reaction-database/ord-schema/pull/595 -- it's suspicious that validation checks are passing @skearnes )

brilee commented 3 years ago

Agreed with [Ir+]. I was initially confused since the pyridines are a charge-neutral ligand, but there's actually an anionic aryl ligand with a direct C-Ir bond, so that makes the overall charge of the iridium center +1.

connorcoley commented 3 years ago

Fixed the Ir, PTAL and approve if it's okay @brilee