Lipshultz Group

Happy 23rd birthday to Juan! 🥳

And, of course, a paper cake to celebrate!

Congrats to Zilu, Yetong, Arshad, Ashley, Jagrut, Noah on their hard work!

Thanks to our collaborators in the Levine Group (SBU Chemistry + IACS), we identified the particularly enabling feature of the scission-promoting excited state: stereoelectronic overlap between O-based radical cation character and the Cα–Cβ bond to be cleaved!

We demonstrate through competition studies that this excited state enforced β-scission is responsible for up to a 1000-fold relative rate enhancement of β-scission, representing true catalyst control over highly reactive alkoxyl radicals!

In particular, electron-deficient catalysts can promote β-scission of alkoxyl radicals which are insufficiently inherently reactive.

Leveraging Divergent Ligand-to-Metal Charge-Transfer Excited State Pathways for Catalyst Control over Alkoxyl Radical Reactivity Ligand-to-metal charge-transfer (LMCT) excitation has emerged in recent years as a powerful modality in organic synthesis, namely for the generation of heteroatom-centered radicals through formal metal–ligand bond homolysis from the LMCT excited state. However, the exploitation of alternative LMCT excited state processes has been extremely limited. Here, we describe a general strategy for tuning the reaction course from LMCT excited states of titanium alkoxides. This reactivity paradigm has been exploited for tandem β-scission/Giese addition reactions of both scission-amenable and scission-recalcitrant alcohols under divergent reaction pathways of metal–ligand bond homolysis and excited state β-scission through judicious choice of electronically tuned Ti catalysts. Through intramolecular competition studies, catalyst-controlled scission is shown to facilitate a rate enhancement of up to 103-fold over the intrinsic scission of free alkoxyl radicals, highlighting the impact of accessing the excited state scission paradigm. Computations support the relevance of a scission-promoting LMCT excited state with stereoelectronically aligned alkoxyl radical cation character to enable direct, selective β-scission.

🎉 Thrilled to share our latest work on Ti-LMCT photocatalysis, out now in @jacs.acspublications.org. We show how Ti-catalysts bearing electronically-differentiated ligands can be leveraged for divergent reaction pathways from the LMCT excited state. Read it here: pubs.acs.org/doi/10.1021/....

two eager, bright-eyed first year graduates standing in a research lab alongside a barely holding it together junior PI

Very excited to welcome two new 1st-year grad students, Juan Perez and Durjay Roy, to the @lipshultzsbu.bsky.social group!

3‐Hydroxy‐4‐pyridinecarboxaldehyde [1849-54-3] C6H5NO2 (MW 123.11) InChI = 1S/C6H5NO2/c8-4-5-1-2-7-3-6(5)9/h1-4,9H InChIKey = NVLPDIRQWJSXLZ-UHFFFAOYSA-N (used as a synthon for certain heterocycles, a ligand precur...

🚨Out now in EROS: an entry on 3-Hydroxy-4-Pyridinecarboxaldehyde. Great to see this published; shout out to Tim for working on it! Now available: doi.org/10.1002/9780....

First minimeeting synthesis workshop of the year! @lipshultzsbu.bsky.social

☃️ Happy holidays and all the best in the new year!! 🥳 A look into our annual hibachi outing 👨‍🍳

Happy Birthday to Vincent! Featuring a cake made by our postdoc Tim

Congratulations to our 2nd years Kiran and Zirui for passing their candidacy exam!!!

Congratulations to Kiran for passing his candidacy exam!! 🥳🥳🥳

Happy belated 30th birthday to our postdoc Tim!! Finally the big 3-0

happy 26th birthday to agniva!! 🎂

🎉 happy 24th birthday to ayah!!!

🚨 NEWS 🚨 Super excited to share that our paper is out now in ACS Catalysis! And, of course, another paper cake 🎉
doi.org/10.1021/acsc...

and #3 — we recently celebrated Ethan’s birthday! 🎉

recap #2 — welcoming Ethan, our new post-doc! he’s joining us after completing his Ph.D. under Liz Jarvo at UC Irvine 👏

summer recaps impending! #1 — may birthdays, celebrating Ashley and Kiran 🥳

🎉🎉🎉 Celebrating Dr. Jagrut Shah!! Congratulations! 🍾

Great job Jagrut! And a rrally great event organized by ACS CVS @lipshultzsbu.bsky.social

Degradative Alcohol Functionalization by Titanocene Photocatalysis Organotitanium complexes are scarcely employed in photocatalytic reactions despite their robust ligand-to-metal charge-transfer photo-chemistry. Herein, we describe the development of titanocene pho-t...

Sharing our 1st preprint on our work on organo-Ti photocatalysis! We've found that titanocenes are photoactive catalysts for alcohol activation by LMCT excitation, enabling β-scission of alkoxyl radicals for degradative functionalization. Congrats Jagrut, Ashley & the whole team!

Congrats to Jagrut for receiving TWO departmental awards for graduating students – the Chemistry Award for Outstanding Doctoral Student and the Chemistry Award for Outstanding Service 🤩🤩

Congrats to Kiran for receiving the Chemistry Award for First-Year Graduate Student Teaching Assistant! 🎉

🍾 Shoutout to Agniva, Ayah, and Vincent for progressing through Second Meeting in their Ph.D. candidacies!!

Incredibly excited to have Jill joining us here at SBU!!

We are looking for a new postdoc to join @lipshultzsbu.bsky.social to work on synthetic methods enabled by catalytic photochemistry of catalyst-substrate complexes! Please apply here by May 8: stonybrooku.taleo.net/careersectio... #chempostdoc

happy belated birthday to yetong!! 🎂🎈