Valence-isomer selective cycloaddition reaction to synthesize functionalized carbocycles DOI Creative Commons
Tetsuhiro Nemoto, Shingo Harada,

Hiroki Takenaka

et al.

Research Square (Research Square), Journal Year: 2023, Volume and Issue: unknown

Published: Sept. 22, 2023

Abstract The rapid and precise creation of complex molecules while controlling multiple selectivities is the principal objective in synthetic chemistry. Combining data science organic synthesis to achieve this goal an emerging trend, but few examples successful reaction designs are reported. We developed artificial neural network regression model using bond orbital predict chemical reactivities. Actual experimental verification confirmed cycloheptatriene-selective (6 + 2)-cycloaddition utilizing nitroso compounds norcaradiene-selective (4 reactions employing benzynes. Additionally, a one-pot asymmetric was achieved by telescoping enantioselective dearomatization non-activated benzenes cycloadditions. Computational studies provide rational explanation for seemingly anomalous occurrence thermally prohibited without photoirradiation.

Language: Английский

Data-driven design of electrocatalysts: principle, progress, and perspective DOI
Shan Zhu, Kezhu Jiang, Biao Chen

et al.

Journal of Materials Chemistry A, Journal Year: 2023, Volume and Issue: 11(8), P. 3849 - 3870

Published: Jan. 1, 2023

In this review, we focus on the systematic construction of data-driven electrocatalyst design framework and discuss its principles, current challenges, opportunities.

Language: Английский

Citations

23
Valence-isomer selective cycloaddition reaction of cycloheptatrienes-norcaradienes DOI Creative Commons
Shingo Harada,

Hiroki Takenaka,

Tsubasa Ito

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: March 14, 2024

Abstract The rapid and precise creation of complex molecules while controlling multiple selectivities is the principal objective in synthetic chemistry. Combining data science organic synthesis to achieve this goal an emerging trend, but few examples successful reaction designs are reported. We develop artificial neural network regression model using bond orbital predict chemical reactivities. Actual experimental verification confirms cycloheptatriene-selective [6 + 2]-cycloaddition utilizing nitroso compounds norcaradiene-selective [4 reactions employing benzynes. Additionally, a one-pot asymmetric achieved by telescoping enantioselective dearomatization non-activated benzenes cycloadditions. Computational studies provide rational explanation for seemingly anomalous occurrence thermally prohibited suprafacial without photoirradiation.

Language: Английский

Citations

7
Unraveling the Bürgi-Dunitz Angle with Precision: The Power of a Two-Dimensional Energy Decomposition Analysis DOI Creative Commons
Israel Fernández, F. Matthias Bickelhaupt, Dennis Svatunek

et al.

Journal of Chemical Theory and Computation, Journal Year: 2023, Volume and Issue: 19(20), P. 7300 - 7306

Published: Oct. 4, 2023

Understanding the geometrical preferences in chemical reactions is crucial for advancing field of organic chemistry and improving synthetic strategies. One such preference, Bürgi-Dunitz angle, central to nucleophilic addition involving carbonyl groups. This study successfully employs a novel two-dimensional Distortion-Interaction/Activation-Strain Model combination with Energy Decomposition Analysis investigate origins angle reaction CN- (CH3)2C═O. We constructed 2D potential energy surface defined by distance between nucleophile carbonylic carbon atom attack followed an in-depth exploration components, including strain interaction energy. Our analysis reveals that emerges from delicate balance two key factors: High energy, as result compound distorting avoid Pauli repulsion, encountered at high angles, thus setting upper bound. On other hand, shaped dominant repulsion when angles are lower. work emphasizes value refined tool, offering both quantitative qualitative insights into reactivity selectivity.

Language: Английский

Citations

11
Controlling Stereoselectivity with Noncovalent Interactions in Chiral Phosphoric Acid Organocatalysis DOI
Isaiah O. Betinol, Yutao Kuang,

Brian P. Mulley

et al.

Chemical Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: March 18, 2025

Chiral phosphoric acids (CPAs) have emerged as highly effective Brønsted acid catalysts in an expanding range of asymmetric transformations, often through novel multifunctional substrate activation modes. Versatile and broadly appealing, these benefit from modular tunable structures, compatibility with additives. Given the unique types noncovalent interactions (NCIs) that can be established between CPAs various reactants─such hydrogen bonding, aromatic interactions, van der Waals forces─it is unsurprising catalyst systems become a promising approach for accessing diverse chiral product outcomes. This review aims to provide in-depth exploration mechanisms by which impart stereoselectivity, positioning NCIs central feature connects broad spectrum catalytic reactions. Spanning literature 2004 2024, it covers nucleophilic additions, radical atroposelective bond formations, highlighting applicability CPA organocatalysis. Special emphasis placed on structural mechanistic features govern CPA-substrate well tools techniques developed enhance our understanding their behavior. In addition emphasizing details stereocontrolling elements individual reactions, we carefully structured this natural progression specifics broader, class-level perspective. Overall, findings underscore critical role catalysis significant contributions advancing synthesis.

Language: Английский

Citations

0
A multifunctional flavoprotein monooxygenase HspB for hydroxylation and C-C cleavage of 6-hydroxy-3-succinoyl-pyridine DOI

Xingyu Ouyang,

Gongquan Liu,

Lihua Guo

et al.

Applied and Environmental Microbiology, Journal Year: 2024, Volume and Issue: unknown

Published: Feb. 28, 2024

ABSTRACT Flavoprotein monooxygenases catalyze reactions, including hydroxylation and epoxidation, involved in the catabolism, detoxification, biosynthesis of natural substrates industrial contaminants. Among them, 6-hydroxy-3-succinoyl-pyridine (HSP) monooxygenase (HspB) from Pseudomonas putida S16 facilitates C-C bond cleavage pyridine ring nicotine. However, mechanism for biodegradation remains elusive. Here, we refined crystal structure HspB elucidated detailed behind oxidative processes. Leveraging structural information about domains binding cofactor flavin adenine dinucleotide (FAD) HSP substrate, used molecular dynamics simulations quantum/molecular mechanics calculations to demonstrate that transfer an oxygen atom reactive FAD peroxide species (C4a-hydroperoxyflavin) C3 substrate constitutes a rate-limiting step, with calculated reaction barrier 20 kcal/mol. Subsequently, hydrogen was rebounded cofactor, forming C4a-hydroxyflavin. The residue Cys218 then catalyzed subsequent hydrolytic process cleavage. Our findings contribute deeper understanding versatile functions flavoproteins transformation nicotine degradation. IMPORTANCE plays pivotal role degrading nicotine, toxic derivative poses significant environmental challenges. This study highlights key enzyme, (6-hydroxy-3-succinoyl-pyridine monooxygenase), breaking down through pyrrolidine pathway. Utilizing dioxygen hydroxylates cleaves substrate’s side chain. Structural analysis structure, combined state-of-the-art computations, reveals its distinctive mechanism. crucial function never discovered homologous enzymes. not only deepen our bacterial degradation but also open avenues applications both cleanup pharmaceutical development.

Language: Английский

Citations

2
Catalysing (organo-)catalysis: Trends in the application of machine learning to enantioselective organocatalysis DOI Creative Commons
Stefan P. Schmid, Leon Schlosser, Frank Glorius

et al.

Beilstein Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 20, P. 2280 - 2304

Published: Sept. 10, 2024

Organocatalysis has established itself as a third pillar of homogeneous catalysis, besides transition metal catalysis and biocatalysis, its use for enantioselective reactions gathered significant interest over the last decades. Concurrent to this development, machine learning (ML) been increasingly applied in chemical domain efficiently uncover hidden patterns data accelerate scientific discovery. While uptake ML organocatalysis comparably slow, two decades have showed an increased from community. This review gives overview work field organocatalysis. The starts by giving short primer on experimental chemists, before discussing application predicting selectivity organocatalytic transformations. Subsequently, we employed privileged catalysts, focusing catalyst reaction design. Concluding, give our view current challenges future directions field, drawing inspiration other domains.

Language: Английский

Citations

2
Photophysical properties of four-membered BN3 heterocyclic compounds: theoretical insights DOI
Manjeet Kumar,

Anagha Kizhake Talakkal,

Ranjan K. Mohapatra

et al.

Journal of Molecular Modeling, Journal Year: 2023, Volume and Issue: 29(11)

Published: Oct. 12, 2023

Language: Английский

Citations

6
Enantioselective Synthesis of Bromodifluoromethyl‐containing Oxazolines by Concerted Lewis/Brønsted Base Catalysis with Chiral Bisphosphine Oxide DOI

Ryo Hirokawa,

Yuki NAKAHARA,

Shotaro Uchida

et al.

Chemistry - An Asian Journal, Journal Year: 2023, Volume and Issue: 18(8)

Published: Feb. 25, 2023

We describe regio- and enantioselective bromocyclization of difluoroalkenes catalyzed by chiral bisphosphine oxides. Owing to the simultaneous activation both brominating reagent amide substrate, desired cyclization reaction proceeds smoothly even at low temperature provide bromodifluoromethyl-containing oxazolines with a quaternary center in highly fashion (up 99% ee). This protocol features use commercially available reagents readily accessible catalysts. The regioselectivity enantioselectivity are influenced catalyst structure, reagent, temperature. Under optimal conditions, 5-exo preferentially compared 6-endo cyclization, depending on electronic properties alkene substrates. A gram-scale synthesis oxazoline was achieved as little 1 mol % catalyst.

Language: Английский

Citations

4
On the gold(I)-catalyzed enantioselective addition of indole to diphenylallene via anion-binding catalysis DOI Creative Commons
Banruo Huang, Binh Khanh, Ulrike Warzok

et al.

Tetrahedron Letters, Journal Year: 2024, Volume and Issue: 149, P. 155247 - 155247

Published: Aug. 13, 2024

Neutral dual hydrogen bond donors (HBDs) are effective catalysts that enhance the electrophilicity of substrates or Lewis/Brønsted acidity reagents through an anion-binding mechanism. Despite their success in various enantioselective organocatalytic reactions, application to transition metal catalysis remains rare. Herein, we report activation gold(I) precatalysts by chiral ureas, leading hydroarylation allenes with indoles. Experimental and computational studies support mechanism for precatalyst activation. Noncovalent interactions were identified as source enantiodifferentiation, providing insights into cooperativity between achiral phosphine ligands ureas.

Language: Английский

Citations

1
Switching Regioselectivity in the Asymmetric Bromocyclization of Difluoroalkenes Catalyzed by a Chiral Bisphosphine Oxide DOI
Yoshitaka Hamashima,

Yuki NAKAHARA,

Ryo Hirokawa

et al.

Synlett, Journal Year: 2023, Volume and Issue: 34(20), P. 2476 - 2480

Published: June 26, 2023

Abstract We present an efficient approach for the enantioselective synthesis of difluoromethylene-containing oxazine compounds through 6-endo-selective bromocyclization difluoroalkenes by using a chiral proton-bridged bisphosphine oxide complex as catalyst precursor. The regioselectivity is significantly influenced solvent and structure, 6-endo cyclization products can be obtained preferentially with moderate to high enantioselectivity. This protocol offers complementary our previously reported 5-exo-selective reaction, permitting diverse medicinally interesting compounds.

Language: Английский

Citations

1