Nature Chemistry, Год журнала: 2024, Номер 16(9), С. 1515 - 1522
Опубликована: Апрель 29, 2024
Язык: Английский
Nature Chemistry, Год журнала: 2024, Номер 16(9), С. 1515 - 1522
Опубликована: Апрель 29, 2024
Язык: Английский
Journal of the American Chemical Society, Год журнала: 2022, Номер 144(14), С. 6185 - 6192
Опубликована: Март 30, 2022
Alcohols and carboxylic acids are among the most commercially abundant, synthetically versatile, operationally convenient functional groups in organic chemistry. Under visible light photoredox catalysis, these native synthetic handles readily undergo radical activation, resulting open-shell intermediates can subsequently participate transition metal catalysis. In this report, we describe C(sp3)–C(sp3) cross-coupling of alcohols through dual combination N-heterocyclic carbene (NHC)-mediated deoxygenation hypervalent iodine-mediated decarboxylation. This mild practical Ni-catalyzed radical-coupling protocol was employed to prepare a wide array alkyl–alkyl cross-coupled products, including highly congested quaternary carbon centers from corresponding tertiary or acids. We demonstrate applications methodology alcohol C1-alkylation formal homologation, as well late-stage functionalization drugs, natural biomolecules.
Язык: Английский
Процитировано
153Chemical Society Reviews, Год журнала: 2023, Номер 52(12), С. 4099 - 4120
Опубликована: Янв. 1, 2023
sp 3 C–H functionalizations under the combination of photocatalytic HAT and transition metal catalysis.
Язык: Английский
Процитировано
98Chemical Science, Год журнала: 2022, Номер 14(2), С. 226 - 244
Опубликована: Ноя. 28, 2022
This review outlines several organic chemistry tasks for which predictive machine learning models have been and can be applied.
Язык: Английский
Процитировано
85Chemical Science, Год журнала: 2023, Номер 14(19), С. 4997 - 5005
Опубликована: Янв. 1, 2023
The lack of publicly available, large, and unbiased datasets is a key bottleneck for the application machine learning (ML) methods in synthetic chemistry. Data from electronic laboratory notebooks (ELNs) could provide less biased, large datasets, but no such have been made available. first real-world dataset ELNs pharmaceutical company disclosed its relationship to high-throughput experimentation (HTE) described. For chemical yield predictions, task synthesis, an attributed graph neural network (AGNN) performs as well or better than best previous models on two HTE Suzuki-Miyaura Buchwald-Hartwig reactions. However, training AGNN ELN does not lead predictive model. implications using data ML-based are discussed context predictions.
Язык: Английский
Процитировано
76European Journal of Organic Chemistry, Год журнала: 2022, Номер 2022(34)
Опубликована: Май 13, 2022
Abstract The opportunity to activate C(sp 3 )−H bonds via homolytic cleavage by means of halogen radicals has long been disregarded in synthetic endeavors due the unpredictable selectivity. Nowadays, photocatalysis established itself as a method choice for generation such reactive intermediates under mild conditions. This Minireview collects recent examples showcasing how photocatalytic manifolds have used tame aggressive Hydrogen Atom Transfer (HAT) purposes. In last section this work, we address site‐selectivity issues posed methodology and show it can be guided through judicious reaction
Язык: Английский
Процитировано
73Nature Communications, Год журнала: 2023, Номер 14(1)
Опубликована: Янв. 9, 2023
Abstract Site- and enantioselective cross-coupling of saturated N -heterocycles carboxylic acids—two the most abundant versatile functionalities—to form pharmaceutically relevant α-acylated amine derivatives remains a major challenge in organic synthesis. Here, we report general strategy for highly site- α-acylation with situ-activated acids. This modular approach exploits hydrogen-atom-transfer reactivity photocatalytically generated chlorine radicals combination asymmetric nickel catalysis to selectively functionalize cyclic α-amino C−H bonds presence benzylic, allylic, acyclic α-amino, α-oxy methylene groups. The mild scalable protocol requires no organometallic reagents, displays excellent chemo-, enantioselectivity, is amenable late-stage diversification, including synthesis previously inaccessible Taxol derivatives. Mechanistic studies highlight exceptional versatility chiral catalyst orchestrating (i) catalytic elimination, (ii) alkyl radical capture, (iii) cross-coupling, (iv) induction.
Язык: Английский
Процитировано
58Journal of the American Chemical Society, Год журнала: 2023, Номер 145(18), С. 9928 - 9950
Опубликована: Апрель 24, 2023
This Perspective surveys the progress and current limitations of nucleophilic fluorination methodologies. Despite long rich history C(sp3)–F bond construction in chemical research, inherent challenges associated with this transformation have largely constrained to a privileged reaction platform. In recent years, Doyle group─along many others─has pursued study development intent generating deeper mechanistic understanding, developing user-friendly reagents, contributing invention synthetic methods capable enabling radiofluorination. Studies from our laboratory are discussed along developments others field. Fluoride reagent implications identity highlighted. We also outline space inaccessible by technologies series future directions field that can potentially fill existing dark spaces.
Язык: Английский
Процитировано
53Journal of the American Chemical Society, Год журнала: 2023, Номер 145(15), С. 8689 - 8699
Опубликована: Апрель 4, 2023
While the oxidative addition of Ni(I) to aryl iodides has been commonly proposed in catalytic methods, an in-depth mechanistic understanding this fundamental process is still lacking. Herein, we describe a detailed study using electroanalytical and statistical modeling techniques. Electroanalytical techniques allowed rapid measurement rates for diverse set iodide substrates four classes catalytically relevant complexes (Ni(MeBPy), Ni(MePhen), Ni(Terpy), Ni(BPP)). With >200 experimental rate measurements, were able identify essential electronic steric factors impacting through multivariate linear regression models. This led classification mechanisms, either three-center concerted or halogen-atom abstraction pathway based on ligand type. A global heat map predicted was created shown applicable better reaction outcome case Ni-catalyzed coupling reaction.
Язык: Английский
Процитировано
50Science, Год журнала: 2023, Номер 380(6646), С. 706 - 712
Опубликована: Май 18, 2023
Catalytic enantioselective methods that are generally applicable to a broad range of substrates rare. We report strategy for the oxidative desymmetrization
Язык: Английский
Процитировано
46Science Advances, Год журнала: 2024, Номер 10(3)
Опубликована: Янв. 17, 2024
Data science is assuming a pivotal role in guiding reaction optimization and streamlining experimental workloads the evolving landscape of synthetic chemistry. A discipline-wide goal development workflows that integrate computational chemistry data tools with high-throughput experimentation as it provides experimentalists ability to maximize success expensive campaigns. Here, we report an end-to-end data-driven process effectively predict how structural features coupling partners ligands affect Cu-catalyzed C–N reactions. The established workflow underscores limitations posed by substrates while also providing systematic ligand prediction tool uses probability assess when will be successful. This platform strategically designed confront intrinsic unpredictability frequently encountered deployment.
Язык: Английский
Процитировано
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