Jisoo Woo
@chemiejisoo.bsky.social
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Ph.D. Candidate at The University of Chicago
reposted by
Jisoo Woo
Mark Levin
6 months ago
A work many years in the making out today in
@jacs.acspublications.org
, where we try to make sense of the structure-reactivity patterns of isodiazenes that refuse to participate in nitrogen deletion: The pyrrolidine rearrangement was particularly useful for pyridazine and piperazic acid synthesis:
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Mechanisms and Synthetic Applications of Cyclic, Nonstabilized Isodiazenes: Nitrogen-Atom Insertion into Pyrrolidines and Related Rearrangements
Reactive intermediates that can promote nonintuitive bond disconnections underpin advancements in skeletal editing methodologies. Accordingly, a detailed understanding of their reactivity and its underlying mechanisms is central to progress in this space. Herein, we catalog and study the reactivity of nonstabilized cyclic isodiazene intermediates generated via the reaction of cyclic secondary amines with an anomeric amide reagent. Depending on the amine structure, distinct and predictable product classes can be accessed: cyclic hydrazones are formed from pyrrolidines, N-amino indoles from indolines, orthoquinodimethane intermediates from isoindolines, cyclopropanes from azetidines, and cyclic tetrazines from piperidines. Mechanistic experiments and density functional theory calculations suggest that many of these transformations proceed through an azomethine imine intermediate. In most cases, this reactive species subsequently rearranges to a cyclic hydrazone by an unusual self-catalysis mechanism proceeding through a dimeric tetrazine. This oxidative nitrogen insertion was leveraged in several subsequent synthetic applications. Redox diversification of the cyclic hydrazones enables access to pyridazines and cyclic hydrazines, including the synthesis of an orthogonally protected l-piperazic acid from the readily available chiral pool l-prolinol.
https://pubs.acs.org/doi/full/10.1021/jacs.5c08361
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reposted by
Jisoo Woo
Mark Levin
6 months ago
Today in
@science.org
,
@mikusp.bsky.social
reports a method to replace the C2 of pyridines with N, affording pyridazines. The change from electronically consonant (pyridine) to dissonant (pyridazine) opens retrosyntheses not typically available to the latter.
www.science.org/doi/10.1126/...
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reposted by
Jisoo Woo
Mark Levin
8 months ago
Fans of Guenther Schlonk will enjoy the "cross-decoupling" easter egg:
jabde.com/wp-content/u...
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reposted by
Jisoo Woo
Mark Levin
8 months ago
Our latest is a serendipitously discovered pair of reactions that can pull either the C2 or C3 carbon out of quinolines by choice of an amine scavenger. A deep mechanistic dive took us some surprising places, in
@chemiejisoo.bsky.social
's latest.
pubs.acs.org/doi/full/10....
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Carbon-Atom Scavengers Enable Divergent, Selective Carbon Deletion of Azaarenes
Divergent synthesis is a powerful strategy that provides simultaneous access to multiple derivatives of a given substrate. However, the emerging developments in skeletal editing have largely delivered...
https://pubs.acs.org/doi/full/10.1021/jacs.5c06577
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reposted by
Jisoo Woo
Mark Levin
10 months ago
If you're interested in a break from the doom-and-gloom, may I recommend our article, online today
@nature.com
A solution to the pyrazole alkylation problem, leveraging S-to-NR atom replacement. Skeletal editing has strategic value, outside of late-stage!
www.nature.com/articles/s41...
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reposted by
Jisoo Woo
Mark Levin
11 months ago
This is the main panel for F32 fellowships for organic chemistry - a pipeline of talent that is being choked off.
add a skeleton here at some point
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reposted by
Jisoo Woo
Shauna Paradine
over 1 year ago
Love to see current and former students meeting each other at conferences! Dynamo 4th year grad student Cay at left and former undergrad Jisoo (who has been rocking it in
@levinchem.bsky.social
's lab) at right, at the Heterocycles GRC
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