CONFPASS: Fast DFT Re-Optimizations of Structures from Conformation Searches DOI Creative Commons
Ching Ching Lam, Jonathan M. Goodman

Journal of Chemical Information and Modeling, Journal Year: 2023, Volume and Issue: 63(14), P. 4364 - 4375

Published: July 10, 2023

CONFPASS (Conformer Prioritizations and Analysis for DFT re-optimizations) has been developed to extract dihedral angle descriptors from conformational searching outputs, perform clustering, return a priority list density functional theory (DFT) re-optimizations. Evaluations were conducted with data of the conformers 150 structurally diverse molecules, most which are flexible. gives confidence estimate that global minimum structure found, based on our dataset, we can have 90% after optimizing half FF structures. Re-optimizing in order energy often generates duplicate results; using CONFPASS, duplication rate is reduced by factor 2 first 30% re-optimizations, include about 80% time.

Language: Английский

Lewis Base–Boryl Radicals Enabled Borylation Reactions and Selective Activation of Carbon–Heteroatom Bonds DOI

Tianyu Peng,

Feng‐Lian Zhang, Yi‐Feng Wang

et al.

Accounts of Chemical Research, Journal Year: 2022, Volume and Issue: 56(2), P. 169 - 186

Published: Dec. 26, 2022

ConspectusThe past decades have witnessed tremendous progress on radical reactions. However, in comparison with carbon, nitrogen, oxygen, and other main group element centered radicals, the synthetic chemistry of boron radicals was less studied, mainly due to high electron-deficiency instability such 3-center-5-electron species. In 1980s, Roberts co-workers found that coordination a Lewis base (amines or phosphines) center could form 4-center-7-electron boryl (Lewis base-boryl LBRs) are be more stable. only limited applications were developed. 2008, Curran achieved breakthrough discovery N-heterocyclic carbene (NHC) which enable range reduction polymerization Despite these exciting findings, powerful valuable LBRs would expected, given structures reactivities easily modulated, provide ample opportunities discover new this Account, summary our key contributions LBR-enabled borylation reactions selective activation inert carbon-heteroatom bonds will presented.Organoboron compounds shown versatile chemical society, their syntheses rely principally ionic The development mechanistically different allows synthesizing products inaccessible by traditional methods. For purpose, we progressively developed series NHC-boryl mediated chemo-, regio-, stereoselective alkenes alkynes, wide variety structurally diverse organoboron molecules successfully prepared. utility borylated also demonstrated. Furthermore, disclosed photoredox protocol for oxidative generation enabled useful defluoroborylation arylboration reactions.Selective bond is an ideal way convert simple starting materials value-added products, while cleavage bonds, particular chemoselectivity control when multiple identical present similar environments, remains long-standing challenge. We envisaged finely tuning properties might solution address Recently, 4-dimethylaminopyridine (DMAP)-boryl promoted sequential C-F functionalization trifluoroacetic acid derivatives, α-C-F selectively snipped via spin-center shift mechanism. This strategy enables facile conversion abundantly available highly mono- difluorinated molecules. Encouraged finding, further three-step sequence construct all-carbon quaternary centers from trichloromethyl groups, where three C-Cl cleaved rational choice suitable precursors each step. dehydroxylative alkylation α-hydroxy carboxylic derivatives achieved, allowing efficient some biomass platform value products.

Language: Английский

Citations

73
Catalytic Approaches to Chemo- and Site-Selective Transformation of Carbohydrates DOI
Kenzo Yamatsugu, Motomu Kanai

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(10), P. 6793 - 6838

Published: April 26, 2023

Carbohydrates are a fundamental unit playing pivotal roles in all the biological processes. It is thus essential to develop methods for synthesizing, functionalizing, and manipulating carbohydrates further understanding of their functions creation sugar-based functional materials. is, however, not trivial such methods, since densely decorated with polar similarly reactive hydroxy groups stereodefined manner. New approaches chemo- site-selective transformations are, therefore, great significance revolutionizing sugar chemistry enable easier access sugars interest. This review begins brief overview innate reactivity carbohydrates. followed by discussions about catalytic enhance, override, or be orthogonal transformation avoids making list reactions, but rather focuses on summarizing concept behind each reported transformation. The literature references were sorted into sections based underlying ideas approaches, which we hope will help readers have better sense current state innovative field.

Language: Английский

Citations

49
Visible light-mediated photolysis of organic molecules: the case study of diazo compounds DOI
Rafael D. C. Gallo, Guilherme Cariello Silva, Tales A. C. Goulart

et al.

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(48), P. 7346 - 7360

Published: Jan. 1, 2023

This article discusses the photochemistry of several diazo compounds undergoing visible light-mediated photolysis to generate free carbenes (or other highly reactive intermediates), which can be sequentially trapped by different reacting partners.

Language: Английский

Citations

48
Transformations of carbohydrate derivatives enabled by photocatalysis and visible light photochemistry DOI Creative Commons

Daniel J. Gorelik,

Shrey P. Desai,

Sofia Jdanova

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(4), P. 1204 - 1236

Published: Jan. 1, 2024

This review article highlights the diverse ways in which recent developments areas of photocatalysis and visible light photochemistry are impacting synthetic carbohydrate chemistry.

Language: Английский

Citations

30
Defluorinative Alkylation of Trifluoromethylbenzimidazoles Enabled by Spin-Center Shift: A Synergistic Photocatalysis/Thiol Catalysis Process with CO2•– DOI
Pei Xu, Xingyu Wang, Zhijuan Wang

et al.

Organic Letters, Journal Year: 2022, Volume and Issue: 24(22), P. 4075 - 4080

Published: June 1, 2022

We describe a catalytic strategy for direct single C(sp3)-F bond alkylation of trifluoromethylbenzimidazoles under photoinduced thiol catalysis process. The CO2 radical anion (CO2•-) proved to be the most efficient single-electron reductant realize such transformation. spin-center shift generated intermediate is key step in realizing C-F activation mild conditions with high efficiency.

Language: Английский

Citations

66
Recent Advances in C–H Functionalisation through Indirect Hydrogen Atom Transfer DOI Creative Commons
Filip S. Meger, John A. Murphy

Molecules, Journal Year: 2023, Volume and Issue: 28(16), P. 6127 - 6127

Published: Aug. 18, 2023

The functionalisation of C–H bonds has been an enormous achievement in synthetic methodology, enabling new retrosynthetic disconnections and affording simple equivalents for synthons. Hydrogen atom transfer (HAT) is a key method forming alkyl radicals from substrates. Classic reactions, including the Barton nitrite ester reaction Hofmann–Löffler–Freytag reaction, among others, provided early examples HAT. However, recent developments photoredox catalysis electrochemistry have made HAT powerful tool capable introducing wide range functional groups into bonds. Moreover, greater mechanistic insights stimulated development increasingly site-selective protocols. Site-selectivity can be achieved through tuning electron density at certain using additives, judicious choice reagent, solvent system. Herein, we describe latest methods functionalizing C–H/Si–H/Ge–H indirect between 2018–2023, as well critical discussion reagents, aspects, substrate scopes, background contexts

Language: Английский

Citations

29
Recent Discovery, Development, and Synthetic Applications of Formic Acid Salts in Photochemistry DOI
Jadab Majhi,

Gary A. Molander

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(4)

Published: Oct. 9, 2023

The advancement of sustainable photoredox catalysis in synthetic organic chemistry has evolved immensely because the development versatile and cost-effective reagents. In recent years, a substantial effort been dedicated to exploring utility formic acid salts various photochemical reactions. this context, formates have demonstrated diverse capabilities, functioning as reductants, sources carbonyl groups, reagents for hydrogen atom transfer. Notably, CO

Language: Английский

Citations

27
Photocatalysts for steering charge transfer and radical reactions in biorefineries DOI
Zhuyan Gao, Puning Ren, Lulu Sun

et al.

Nature Synthesis, Journal Year: 2024, Volume and Issue: 3(4), P. 438 - 451

Published: March 26, 2024

Language: Английский

Citations

17
Boryls, their compounds and reactivity: a structure and bonding perspective DOI Creative Commons
Xueying Guo, Zhenyang Lin

Chemical Science, Journal Year: 2024, Volume and Issue: 15(9), P. 3060 - 3070

Published: Jan. 1, 2024

Boryls and their compounds are important due to diverse range of applications in the fields materials science catalysis. They an integral part boron chemistry, which has attracted tremendous research interest over past few decades. In this perspective, we provide in-depth analysis reaction chemistry boryl from a structure bonding perspective. We discuss reactivity boryls various transition metal complexes diborane(4) towards different substrate molecules, with focus on nucleophilic electrophilic properties processes. Additionally, briefly radicals. Our sheds new light unique potential for catalytic applications.

Language: Английский

Citations

10
C2-ketonylation of carbohydrates via excited-state palladium-catalyzed 1,2-spin-center shift DOI Creative Commons
Gaoyuan Zhao, Upasana Mukherjee, Ling Zhou

et al.

Chemical Science, Journal Year: 2022, Volume and Issue: 13(21), P. 6276 - 6282

Published: Jan. 1, 2022

C2-ketonyl-2-deoxysugars, sugars with the C2-hydroxyl group replaced by a ketone side chain, are important carbohydrate mimetics in glycobiology and drug discovery studies; however, their preparation remains vital challenge organic synthesis. Here we report first direct strategy to synthesize this class of glycomimetics from readily available 1-bromosugars silyl enol ethers via an excited-state palladium-catalyzed 1,2-spin-center shift (SCS) process. This step-economic reaction features broad substrate scope, has high functional tolerance, can be used late-stage functionalization natural product- drug-glycoconjugates. Preliminary experimental computational mechanistic studies suggested non-chain radical mechanism involving photoexcited palladium species, 1,2-SCS process, Mizoroki-Heck reaction.

Language: Английский

Citations

33