***We are hiring!***
My group is looking for a postdoc with comp chem experience to join us at
@UTDallasChemBio
from August '24.
You can find out more about the position and submit your application here:
Please share!
#compchem
Check out "Mechanistic insights into the origins of selectivity in a Cu-catalyzed C–H amidation reaction", now on
@ChemRxiv
().
My second contribution as part of the
@mhg_group
, with beautiful kinetics from Nico Ciccia and Yifan Guo from the
@HartwigGroup
Check out "Mechanistic insights into the origins of selectivity in a Cu-catalyzed C–H amidation reaction", now on
@ChemRxiv
().
My second contribution as part of the
@mhg_group
, with beautiful kinetics from Nico Ciccia and Yifan Guo from the
@HartwigGroup
My entry to the
#RSCPoster
Twitter conference: How an understanding of electron delocalisation in strained molecules can be used to guide the synthesis of caged compounds for drug discovery. (1/6)
After 8 years I'm sadly saying goodbye to Oxford. Thank you to all who made my time here so special, especially
@fjduarteg
,
@EdAndersonGroup
, and too many others to mention here. Looking forward to my next adventure in Berkeley with the
@mhg_group
!
Excited to share that Alistair's (
@ASterlingChem
) work on the electronic structure and reactivity of [1.1.1]propellane has just been accepted for publication in
@ChemicalScience
! You can read the open-access article here:
#compchem
Delocalisation can be used hand in hand with strain release to both understand and predict the reactivity of organic molecules. Very happy to be able to share the central ideas developed during my PhD:
#compchem
Reactions that release strain energy are found everywhere in chemistry, but the link between strain and reactivity doesn’t hold for even simple systems, e.g. cyclopropane, cyclobutane and [1.1.1]propellane release similar strain energy, but reactivity differs hugely. (1/5)
Really happy to have been selected to attend the Global Young Scientists Summit in January 2021 - looking forward to meeting and learning from eminent scientists and early-career academics from around the world
#GYSS
Straining to React: Delocalization Drives the Stability and Omniphilicity of [1.1.1]propellane by Alistair Sterling, Russell C. Smith, Edward Anderson & Fernanda Duarte
Had a great time working on this project with
@romain_costil
and
@JonathanClayden
- using a combination of MD / DFT (by
@fjduarteg
), NBO, coupled cluster calculations, and a predictive model based on Charton steric parameters to understand the origins of atropisomerism
#compchem
Interested in chemical bonding? Check out this
@ChemistryWorld
collection featuring an opinion piece on my recent work with
@mhg_group
about the importance of orbital nodes ()
Updated preprint of our work on [1.1.1]propellane - just hit 2000 article views and >500 downloads! If you're interested in the interplay between electron correlation and symmetry, and how this defines the behaviour of a strange but surprisingly useful molecule, have a read!
Excited to share our review of advances in computational techniques for the prediction of selectivity in organocatalysis. We track the evolution of the field from transferrable empirical models, through to accurate QM simulations, and onwards to descriptor-based ML models.
Our review on developments in predictive models for organocatalysis is out now in
@WIREs_Reviews
- covering the state of the art in the field from early qualitative models to QM and ML descriptor-based predictive models.
Shocked and disgusted by the now infamous "article" published by
@angew_chem
. We privileged majority have to stand up to this blatant sexism and racism, and support our friends and colleagues who experience this every day. I can't begin to imagine the emotional burden.
Congrats
@1999Nils
and the team! I'm lucky to have worked with such talented people, especially Nils for his tireless synthetic and computational work. It's really rewarding to see a prediction from my PhD on 111P vs 311P reactivity turn into something so exciting
#compchem
"Attending" the Small Organic Molecules day from the comfort of my kitchen - very interesting talks so far from
@reymondgroup
and Markus Meringer.
Live stream is here:
#compchem
If you're at
#ACS
Fall this week and interested in physical organic chemistry, possible origins of covalent bonding, or organometallic chemistry, I'll be talking about each of these topics (1/4)
Excited to share a new method for the asymmetric synthesis of BCPs from [1.1.1]propellane and simple aldehydes using photoredox organocatalysis!
#compchem
(1/4)
Rationalizing the diverse reactivity of [1.1.1]propellane through σ–π-delocalization by Edward A. Anderson, Fernanda Duarte et al. is on our back cover this week 😃
Read it here 👉
#ChemSciCovers
@joaquinbarroso
In many cases, B3LYP is certainly adequate. The problem is that without a benchmark study, there is no way of knowing when it gives an answer that is qualitatively wrong. This is of course not unique to B3LYP. Benchmarking is good science.
a „quick project“ that turned into a huge study on the reactivity of strained radicals and benzylic radicals in general. Learned loads of fundamental chemistry along the way too🤓 It was great fun to work again with
@ASterlingChem
and
@fjduarteg
@TYoungResearch
However you like - as long as your definition lets you to make predictions of behaviour for a wide range of diverse systems (perhaps?)
Exceptions can be found for every rule when not dealing with observables, but if the rule is useful 99% of the time then why throw it out?
Happy to say I have passed my DPhil viva, and am grateful to
@benwansell
and Jim Snyder for their super helpful comments. Enormous thanks to
@aeggers
for his patient guidance, and to many others who helped me along the way. Excited to join colleagues at
@Durham_SGIA
from Aug.!
You can read our
@ChemicalScience
article on [1.1.1]propellane reactivity here:
And our
@ACSCatalysis
article on photoredox BCP synthesis here:
Thanks for reading! (6/6)
Exciting recent work from Albrecht, Peña, Gross & co () on single-molecule reaction selectivity in this week's
@mhg_group
journal club – discussions ranging from Bergman cyclisations, to the (un)observability of orbitals, & JT-induced charge/spin separation
Check out our latest BCP work: A way to directly couple BCP iodides with aryl Grignards. Nice work
@JNugentChem
, Beth and the BCP team!
Synthesis of All-carbon Disubstituted Bicyclo[1.1.1]pentanes by Fe-Catalyzed Kumada CrossCoupling via
@figshare
Fantastic to see this paper out from
@DonohoeGroup
@duarte_group
. I'd like to highlight the computational work from Part II student Jacky Sze – he did this work fully remotely from HK (with a 7 hour time difference!) during the pandemic. No mean feat!
Check out Tom (
@TYoungResearch
) and Razvan's work on the automation of metallocage self-assembly and binding calculations, now on
@ChemRxiv
! You can try it out yourself with our shiny new web app here:
#compchem
@radscientist_
My all time favourite is the Ohira-Bestmann modification of the Seyferth-Gilbert homologation because it's such a cool mechanism, with a close second of the Morita-Baylis-Hilmann reaction (added bonus that it's been at the centre of computational controversy)
@EdAndersonGroup
is delighted to share our Perspective on the beautiful BCP framework in
@JACS_Au
. Congratulations
@BethanyShire
on this article! See:
Conquering the Synthesis and Functionalization of Bicyclo[1.1.1]pentanes
We construct a simple kinetic energy decomposition scheme that disentangles electron delocalization effects from orbital relaxations, revealing an important effect that we call 'node-induced electron confinement', which occurs when valence orbitals with a node overlap.
(2/3)
Great talk today from Thomas Kaiser (Emory University) on the use of machine learning in drug development - 14 to 28 years-worth of hit-to-lead development in just a year
The resulting theory is used to look at classic periodic trends in bond strengths, revealing a fine balance of delocalizing and localizing effects that combine to sometimes strengthen, and sometimes weaken, chemical bonds.
(3/3)
We have a funded
#compchem
PhD position
@duarte_group
@OxfordChemistry
to start in Oct 2022. This exciting project w/
@ASTRAZENECAUK
focuses on the development of computational tools to guide reaction optimisation/catalyst design. Please RT, deadline 25/03
Since then, we've been interested in the enantioselective installation of BCPs to achiral substrates. We're excited to share the results of these efforts very soon! (5/6)
@TYoungResearch
Looking at the problem you have, and how rare it is you get a molecule that doesn't obey your distance criterion, could you have a flag for pathological cases where you define the bonds you want manually? Either by submitting a custom bond order matrix, or a list like in NBO?
There's also an unusual dependence of enantioselectivity on the photocatalyst, which could indicate that C-C bond formation is not the enantiodetermining step. We instead suggest that the enamine E/Z ratio and relative oxidation rates determine the observed selectivity. (3/4)
Alongside this work, we designed a mild photoredox reaction to generate a wide range of BCPs from [1.1.1]propellane, including biomolecules and pharmaceutical derivatives. Mechanistic studies revealed a photoredox-initiated chain process. (4/6)
Using computation, we found that the electron density that should be localised in the interbridgehead C–C bond is actually partially delocalised onto the methylene bridges. This delocalisation explains the stability of [1.1.1]propellane, and its reactivity. (3/6)
We looked at the origins of enantioselectivity, and found that substrate/organocatalyst non-covalent interactions are crucial for blocking one face of the radical. (2/4)
At 5.40pm on Monday at the Chemical Bonding Theory session (Room 205, South Bldg., Moscone Center) I'll share some new results about the roles of delocalization and orbital contraction on the formation of covalent bonds (3/4)
We want to design new reactions to make bicyclopentanes (BCPs), because they're useful sp3-rich structures for drug discovery (and more). We think the best way to do this is from [1.1.1]propellane. Its reactivity profile was poorly understood, so we wanted to change that. (2/6)
@TrevorAHamlin
Thanks! We think ∆E(int) > 0 because the cage can't distort enough to overcome repulsion between the anion and the e- rich cage at the TS. We've done the analysis along the reaction coordinate and it is consistent with this view. Open to any suggestions you might have!
@MustLoveScience
Orange-tinted specs made a huge difference when doing quantum yield measurements in a dark room - would have been unbearable without them
If you like radical clocks, polytopal rearrangements, Hammett plots, and questions about Cu–C covalency, then maybe you'll like our paper!
@UCB_Chemistry
@BerkeleyLab