One programming model to rule them all: High-performance computational chemistry and applications via OpenMP offloading mode DOI Open Access
Melisa Alkan

Опубликована: Янв. 1, 2023

This dissertation is focused around enabling large-scale quantum chemistry calculations by developing novel algorithms on new heterogeneous hardware architectures. Section 2 contains a study assessing the importance of many-body dispersion phenomena in molecular clusters and understanding need to incorporate into existing methods accurately capture long-range interactions. It known that highly accurate are computationally expensive; therefore, there for computer will be able vastly improve time solution enable correlated large systems. Sections 3 4 focus development implementation various molecules unprecedent sizes. Specifically, describes CUDA-based algorithm enables GPU-acceleration main parts Self-Consistent Field (SCF) cycle, resulting fastest SCF code date. introduces OpenMP-based Fock build formation, which GPU-accelerated all GPU CPU hardware. 5 expands upon OpenMP work library named LibERI evaluating integrals – often computational bottleneck many methods. intended serve as fast can interfaced with any software packages through MolSSI Driver Interface (MDI). MDI standard interface between scientific codes. One LibERI's objectives seamlessly integrate Molecular Mechanics (MM) package using QM/MM calculations. integration would allow efficient treatment QM regions via LibERI. Lastly, 6 concludes this applies unravel mechanism Pd-catalyzed carboacylation reaction involving activation ester C-O bonds.

Язык: Английский

Nickel-Catalyzed 1,1-Aminoborylation of Unactivated Terminal Alkenes DOI Creative Commons
Laura Talavera, Robert R. A. Freund, Huihui Zhang

и другие.

ACS Catalysis, Год журнала: 2023, Номер 13(8), С. 5538 - 5543

Опубликована: Апрель 10, 2023

Herein, we disclose a Ni-catalyzed 1,1-difunctionalization of unactivated terminal alkenes that enables the incorporation two different heteroatom motifs across an olefin backbone, thus streamlining access to α-aminoboronic acid derivatives from simple precursors. The method is characterized by its simplicity and generality wide number coupling counterparts.

Язык: Английский

Процитировано

21
Diverse Synthesis of C-Glycosides by Stereoselective Ni-Catalyzed Carboboration of Glycals DOI
Mao‐Yun Lyu, Samuel A. Jacobo, M. Kevin Brown

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(28), С. 18866 - 18872

Опубликована: Июль 5, 2024

C-Glycosides are important structures that common to natural products and pharmaceutical agents. Established methods for their synthesis involve the reaction of an activated anomeric carbon. In this study, we report a conceptually new approach involves stereoselective Ni-catalyzed carboboration glycals. these reactions, not only is C–C bond formed at carbon, but synthetically useful C–B also installed. Upon oxidation, differentially protected C-glycosides be formed. addition, stereospecific manipulation leads diverse C-glycosides. Finally, application method in established C-glycosides, such as C-glycosyl amino acids, well strategy make all possible diastereomers C1 C2.

Язык: Английский

Процитировано

7
Recent Advances in Ni‐Catalyzed 1,1‐Difunctionalization of Unactivated Olefins DOI Open Access
Álvaro Velasco‐Rubio, Rubén Martı́n

Advanced Synthesis & Catalysis, Год журнала: 2023, Номер 366(4), С. 593 - 602

Опубликована: Дек. 7, 2023

Abstract Unactivated olefins rank amongst the most important feedstocks in organic synthesis. Their availability makes them particularly useful synthons for subsequent functionalization, a catalytic manner. Driven by popularity ascribed nickel catalysis as new tool to rapidly forge molecular architectures via one‐or two‐electron manifolds, recent years have witnessed significant advances Ni‐catalyzed olefin difunctionalization. While 1,2‐difunctionalization or remote functionalization “chain‐walk” become mature disciplines repurposing potential of building blocks, it was only recently that extensions this chemistry 1,1‐difunctionalization been possible. This review summarizes 1,1‐difunctionalization, holding considerable promise powerful strategy our ever‐growing synthetic repertoire.

Язык: Английский

Процитировано

12
Approach Toward Stereoselective α‐Arylation by Pd/Cu‐Catalyzed Arylboration of Electron Deficient Alkenes DOI Creative Commons
Suman Das,

Michael Reilly,

Stanna K. Dorn

и другие.

Angewandte Chemie International Edition, Год журнала: 2025, Номер unknown

Опубликована: Март 27, 2025

Abstract Palladium‐catalyzed cross coupling of enolates—α‐arylation—is an established method for chemical synthesis. A major challenge in the field is control stereochemistry α‐carbon. This typically due to facile epimerization under basic reaction conditions α‐arylation. In this study, alternative approach presented that involves Pd/Cu‐catalyzed arylboration electron deficient alkenes. The products are generated with high levels diastereoselectivity a broad range substitution patterns. Enantioselective variants also addition product derivatizations.

Язык: Английский

Процитировано

0
Approach Toward Stereoselective α‐Arylation by Pd/Cu‐Catalyzed Arylboration of Electron Deficient Alkenes DOI Creative Commons
Suman Das,

Michael Reilly,

Stanna K. Dorn

и другие.

Angewandte Chemie, Год журнала: 2025, Номер unknown

Опубликована: Март 27, 2025

Abstract Palladium‐catalyzed cross coupling of enolates—α‐arylation—is an established method for chemical synthesis. A major challenge in the field is control stereochemistry α‐carbon. This typically due to facile epimerization under basic reaction conditions α‐arylation. In this study, alternative approach presented that involves Pd/Cu‐catalyzed arylboration electron deficient alkenes. The products are generated with high levels diastereoselectivity a broad range substitution patterns. Enantioselective variants also addition product derivatizations.

Язык: Английский

Процитировано

0
Stereoselective Construction of Multifunctional C-Glycosides Enabled by Nickel-Catalyzed Tandem Borylation/Glycosylation DOI
Xiaomei Wu, Shijia Li, Liqin Chen

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(32), С. 22413 - 22423

Опубликована: Авг. 3, 2024

Stereochemically pure saccharides have indispensable roles in fields ranging from medicinal chemistry to materials science and organic synthesis. However, the development of a simple, stereoselective, efficient glycosylation protocol access α- β-C-glycosides (particularly 2-deoxy entities) remains persistent challenge. Existing studies primarily focused on C1 modification carbohydrates transformation glycosyl radical precursors. Here, we innovate by harnessing situ generated glycosyl-Ni species achieve one-pot borylation cascade manner, which is enabled an earth-abundant nickel-catalyzed carboboration readily accessible glycals without any ligand. This work reveals potential for modular multifunctional platform facilitate simultaneous introduction C-C C-B bonds at stereogenic center saccharides, largely unexploited research area. Preliminary experimental computational indicate that endocyclic O C3 group play important stereoseclectively forging glycosidic bonds. As result, diverse range C-R (R = alkyl, aryl, alkenyl) 2-deoxygenated glycosides bearing modifiable boron groups could be rapidly made with excellent stereocontrol exhibit remarkable functional tolerance. The synthetic underscored late-stage natural products commercial drugs as well facile preparation various rare sugars, bioactive conjugates, key intermediates prorocentin, phomonol, aspergillide A.

Язык: Английский

Процитировано

3
Pd(0)-Catalyzed Diastereoselective and Enantioselective Intermolecular Heck–Miyaura Borylation of Internal Enamides for the β-Aminoboronate Ester Synthesis DOI
Chenchen Wang,

Yang Xi,

Tingting Xia

и другие.

ACS Catalysis, Год журнала: 2023, Номер 14(1), С. 418 - 425

Опубликована: Дек. 20, 2023

Miyaura borylation is widely recognized as one of the most reliable methods for constructing an organoboron compound. Reported herein Pd(0)-catalyzed asymmetric three-component Heck–Miyaura with interception internal olefin, aryldiazonium salt, and diboron reagent. This Heck-triggered protocol proceeds in a highly chemoselective, diastereoselective, enantioselective manner, thus allowing expedient construction 1,2-diaryl substituted β-aminoboronate esters derivatives vicinal stereogenic centers. The versatility resulting benzylic boronic allows their further transformation to more-intricate chiral amines.

Язык: Английский

Процитировано

6
Recent Advances in Nickel-Catalyzed C-C Cross-Coupling DOI
Yangyang Li, Jiao Long,

Guoyin Yin

и другие.

Topics in organometallic chemistry, Год журнала: 2023, Номер unknown, С. 181 - 231

Опубликована: Янв. 1, 2023

Язык: Английский

Процитировано

4
Synthesis of (±)-Phyltetralin by Cu/Pd-Catalyzed Arylboration DOI
Grace L. Trammel,

Abby C Kerlin,

Christian Zachau

и другие.

Synlett, Год журнала: 2023, Номер 34(18), С. 2197 - 2199

Опубликована: Апрель 5, 2023

A synthesis of (±)-phyltetralin is reported. Notable features the include a diastereoselective Cu/Pd-catalyzed arylboration reaction and Matteson homologation.

Язык: Английский

Процитировано

2
Mechanism and Origins of Regio- and Stereoselective Alkylboration of Endocyclic Olefins Enabled by Nickel Catalysis DOI
Man Chen,

Yi-Wen Gu,

Wei Deng

и другие.

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(19), С. 14115 - 14130

Опубликована: Сен. 28, 2023

The Ni-catalyzed alkylboration of endocyclic olefins is a stereo- and regioselective approach for the synthesis boron-containing compounds. We report detailed density functional theory (DFT) study to elucidate mechanism origins stereo-, chemo-, regioselectivity enabled by nickel catalysis. proceeds via migratory insertion alkenes, β-H elimination Ni(II) complex, subsequent leading new combined with an alkyl radical, reductive eliminations. electronic effects synergistically control toward C1- C2-position boration. In C1-position boration, more electron-deficient carbon atom tends combine electron-rich -Bpin group leads boration products. stereoselectivity influenced solvent effect, interaction between substrate groups, low-polarity 1,4-dioxane, favorable steric hindrance effect result in cis-alkylboration product. Chemoselectivity 1,3-alkylboration results from group.

Язык: Английский

Процитировано

2