✨Our new concept in @ACSCatalysis was featured as a cover!☯️🌘 Not dHAT, not iHAT.. in between: PET-HAT!🐈🎩 Upon Photoinduced Electron Transfer:🌗reduction of a substrate on the light moon side, the CATalyst scratches apart a C-H bond w/ its dark side🌓N(yan)-centered radical! – at Milngavie, Scotland

Many congratulations🎉🎊🙏 to the team; @luigidolcini & Alex (paper #1 of his PhD!), & especially to 1st-author @m_lepori (a.k.a. "Dr. Ritter") for his first (co)-corresponding⭐️article! Prost!🍻

By 1-electron logic, one can generate & add radicals to alkenes, then trap the resulting radicals w/ an O atom source, rapidly building complexity in 3-component reactions, often under milder conditions. We review this &dissect the review into O atom source: tBuOOH, DMSO, or O2🫧

Classically, there's of course many ways to make ketones w/ 2-electron logic. To make them directly from cheap feedstock alkenes often requires harsh conditions⚠️, e.g. T.M./strong acid🧪catalyzed hydration(+[O]), or Wacker-type chemistry, or ozonolysis ..Is there a better way?🤔

🚨New review!📰(BarhamLab on🔥) Streamlined⏩access to complex ketones in 1 synthetic step: We review latest advances in 3-comp. alkene 1,2-oxo-functionalizations. 1e- logic unlocks access to a broad pool of radical precursors &O atom sources to play with🤹‍♂️tinyurl.com/mr2akdrp

Congrats🎉to former postdoc Xianhai (now Ass. Prof. in Xiamen!🤩) for discovering/scoping catalysis, Wolfgang/Ahmed/Erling for SEC/emission, Simon/Sam/Dan for testing *PC(.-), Binoy/Ryan for TA, Mark/Bob for DFT, Jonathan/Daria for synthesis ..Another big fish for 2026 guys!🎣

While XEC rxns = hard for any PRC platform (hats off to Ni/electro🫡), we envision developing dyad PCs to challenge✊any coupling of e-rich+e-poor partners. Watch out Suzuki/Heck/Sonogashira! Knowing how tempting the 'dark side' of cross-coupling is- let this be a ray of light!🌥️

We're really psyched🤩by the unique✨temporal control organoPC dyads offer- we believe dyads can be engineered to generate &couple radicals faster than they 'clock' (ie 5-exo-trig cyc/cyclopropyl opening). Stereoretentive couplings👐could even be possible, with no ligand/metal🚫.

2) the first *direct*🔎observation of preassembly-directed PET of an organic PC(.-), via TA-detection📸of its post-PET exciplex. 'til now, previous studies (incl. ours!) rely on indirectly invoking preassembly via quenching of ps-lived ESAs/kinetic arguments. Seeing👁️=believing!

The study's nuances break mechanistic ground in radical anion photocatalysis too: We report 1) the first i) redox-neutral, convergent conPET: Both intermediates incorporated into a single product in high (~75-95%) A.E.🌱'til now, the e-donor substrate is consistently sacrificed🚮

What's really cool compared to previous photocatalysts& their conditions: 1) NO homocoupling of *either* radical🖇️& no hydro-de-X (known in prev. studies)! 2) NO covalent trapping of radicals by scavengers! Rate📉slows down but final yields unaffected even upto 4 equivs TEMPO!🤯

The beauty of this platform is the simplicity of conditions: both substrates can be used in 1 equiv, ~1 mol% organoPC, hv, solvent-that's it! NO need for technical complexity of electrophoto🔋💡A dyad brings multiple sites for redox&binding; can do as challenging redox (>-2.6 V).

OrganoPC dyads i) chemoselectively forge⚒️sp-sp3/sp-sp3/sp-sp2 bonds ii) late-stage modify complex mols/drugs💊iii) divert🔀mechanism from conPET via binary *PC(.-) assembly [ArX partially tolerated] to ternary *D(.+)-A(.-) EDA assembly by simply changing D [ArX fully tolerated!]

Moreover, while we as a community are good at generating & handling Ar(.) (~150ns) & Csp3(.) (~microseconds), higher s-character radicals (vinyl/sp; ~0.3-30 ns)⏱️are rarely possible to capture in cross-coupling & require intramolecular cyclization or T.M.🪙(eg Au/Ni/Fe) trapping.

Cross-(hetero)coupling🪢of 2 radicals is kinetically unlikely as it is, vs radicals meeting neutrals/homocoupling🖇️. In absence of T.M.s(Ni/Fe), only works when one radical's lifetime is several orders of magnitude more than another (a persistent radical that doesn't homocouple).

🚨After 5y in making, unveiling a special discovery🌌in @Chem_CP: Cross-coupling transient(vinyl/sp!) radicals.🚫Ni/Fe/radical sorting/hydrazides.✅Covalent-rotating organoPC💡dyads template 2 precursors, generate& cross-couple radicals in close proximity tinyurl.com/mtkd45p4

You're totally right, they prob just brew coffee. Blackmond only holds a chair at Scripps & Bures is just hanging out as ICREA Prof.—totally unheard of outside a local pub.. ..except to literally anyone who ever opened a journal or studied reaction kinetics in the last 2 decades

Not to worry - a Blackmond/Bures prize on RPKA & VTNA is surely 'brewing' 😎 While I do share the sentiment: there was even an example of non-linear effects in asymm. synth 4 years prior to Soai's 1995 paper, by an industrial chemist Rautenstrauch, who is still alive..🤔

僕は彼をノーベル賞候補の一人だと思っています。彼は、2008年の光レドックス触媒反応における「ルネサンス」の何十年も前から、先駆的な貢献を果たしていたからだ。退職後に移られた韓国の「EWHA」で、彼にお会いする機会がありました。私も実際にお会いして、本当に素晴らしい先生だと思いました！🤩

..Perhaps I can add another related to photocatalysis - hopefully Prof. Shunichi Fukuzumi might also be recognized for the inevitable future prize for photoredox catalysis?🤞